Non-adhesive latex products

ABSTRACT

The object of the present invention is to provide a non-adhesive clean latex product and a method for manufacturing the same. A non-adhesive clean emulsion latex product is manufactured by adding a carboxyl-group blocking agent to a carboxylated latex or by providing a layer treated with the carboxyl-group blocking agent on one or both surfaces of a film of the carboxylated latex. Further, a non-adhesive, easy-to-wear-and-remove emulsion latex product is manufactured by affording a layer treated with a carboxyl group blocking agent on the inside surface of a carboxylated latex film and providing a chlorination treatment on the outside thereof. Furthermore, a sulfur-free, highly durable latex product can be manufactured by adding an aluminate or an aluminumhydroxide gel to the latex. The present invention also provides a non-powdered, clean, on-machine wound fingerstall.

TECHNICAL FIELD

[0001] The present invention relates to a novel non-adhesivecarboxylated latex product, and to a novel process for manufacturing thesame. Further, the present invention provides a latex product with highdurability on wear.

BACKGROUND ART

[0002] Carboxylated latex products—for example, dipping products such asballoons, gloves, fingerstalls and condoms; extruded products such asrubber threads and rubber pipes; cast-molded products such as balloonsand toys; and whole rubber products and products having rubber surfacesuch as rubber sheets, hoses and draw cloths—are apt to have adhesivesurfaces to result in damaging the processability of the products orproducing defective articles. Further, they have the defect in thatproducts having desirable shapes cannot be fabricated.

[0003] Heretofore, to overcome these defects, adhesion preventing agentshave been used, and as the adhesion preventing agents powderedsubstances are normally used, which are called dusting powder (or simplypowder) . As the powder, generally used are mica, talc, calciumcarbonate, white carbon and corn starch.

[0004] The powder, however, spreads to an article in contact with thelatex product and becomes a cause of various troubles if the articlebelongs to the field of precision instrument. Also, appearance of thelatex product is damaged. In July 1999, FDA issued a regulation onmedical rubber gloves that the powder quantity on synthetic rubbermedical gloves should be controlled 120 mg or less per piece of gloves.On the other hand, as to natural rubber medical gloves, the regulationwas issued that controlled the soluble protein to 1200 μg per piece ofgloves to prevent the latex allergy derived from protein. And, a shiftfrom natural rubber gloves to synthetic rubber gloves is anticipated.Thus, making the synthetic rubber products non-adhesive is an importanttechnical issue of the field.

[0005] The general method of adhesion prevention other than the powderincludes halogenation by post-chlorination treatment. For example, U.S.Pat. Nos. 3,411,982 and 3,740,262 disclose that halogenation makes thesurface of rubber gloves slippery. U.S. Pat. No. 4,304,008 discloseshalogenation, in place of the powder, facilitates wearing rubberproducts. U.S. Pat. No. 3,740,262 discloses halogenating gloves toprovide the outside surface without the powder and the inside surfacewith the powder.

[0006] The halogenation is a method in which a thin layer of halogenatedrubber is made on the product surface to prevent adhesion and blooming,and this method is fairly widely conducted, providing a rubber producthaving a clean surface without the powder. However, when the degree ofhalogenation is too high, discoloration occurs, the surface becomesbrittle to cause cracks, or heat resistance is deteriorated. Further, itis feared for the contacting metal to be corroded. Above all things,many users hesitate to use such products because of their beingenvironmentally undesirable.

[0007] U.S. Pat. No. 4,304,008 discloses surgical gloves wherein theinside layer comprises a natural rubber and the outside layer ahalogen-resistant silicone, the inside layer being halogenated to give anon-adhesive property.

[0008] The defect of halogenation is admitted by U.S. Pat. No.5,284,607. In the patent, medical gloves are formed using anacid-soluble powder, which is then dissolved by treating with an acidsuch as nitric acid, and thereafter the gloves are chlorinated by ableaching agent.

[0009] There are found a variety of improvements in the methods ofmanufacturing rubber products which use powders or substances havingparticulate structures.

[0010] U.S. Pat. No. 4,070,713 discloses medical gloves comprising twolayers, i.e., outside and inside layers, of elastic substances. In theinside layer a particulate substance such as zinc oxide on titaniumoxide is firmly embedded, and moreover on the inside surface to come incontact with the skin, the particles are exposed partially.

[0011] U.S. Pat. No. 4,143,109 discloses a manufacture method relatingto the above-mentioned patent.

[0012] U.S. Pat. No. 5,138,719 discloses a method for making powder-freegloves, fingerstalls and the like from latex and microcapsule. Themicrocapsule is dispersed and distributed in the latex so that itsconcentration may increase from the outside surface of the producttoward the inside surface thereof to build a concentration gradient. Themicrocapsule concentration is high on the inside surface, and this givesa good slipping property and an easy wearing without the powder.

[0013] U.S. Pat. No. 5,881,386 discloses gloves with the two layerscomprising polyvinylchloride and polyesterpolyurethane. The insidepolyesterpolyurethane layer is incorporated with a particulate substanceof 1 to 75 μm.

[0014] Japanese Patent Application Laid-Open (Kokai) No.11-12823discloses, regarding the working gloves for clean room manufactured frompolyvinylidene chloride paste sol, a technology of manufacturing workinggloves with improved dusting properties by dipping them in an insidesurface treating agent containing a powder of 0.1 to 1.5 μm followed bydrying.

[0015] Japanese Patent Application Laid-Open (Kokai) No.11-61527discloses rubber gloves excellent in wearing and removing which areprovided with a slippery resin layer by dipping in an aqueous dispersingliquid containing a synthetic rubber latex that is not coagulated by acoagulant contained in gloves themselves and containing an organicfiller.

[0016] Japanese Patent Application Laid-Open (Kohyo) No.9-501983discloses a water-dispersable silicone modified dispersion powdercomposition and the method of manufacturing it, and describes that thecomposition can be used as antiblocking agent.

[0017] In recent years, such products have come to be developed thatvarious substances are coated on the surface of latex products.

[0018] U.S. Pat. No. 4,310,928 provides surgery gloves by dispersing anoil and fat or lipophilic substance in a coagulation liquid and coatingit on the surface of a natural rubber. Here, to prevent separation ofthe oil and fat or lipophilic substance, a surface active agent is addedin the coagulation liquid.

[0019] U.S. Pat. Nos. 5,780,112 and 5,974,589 disclose a method ofattaching a high density straight-chain hydrocarbon polymer, especiallypolyethylene, to the surface of a natural rubber by chlorine generatedby acidifying a hypochlorite, and the latex product thus treated isnon-adhesive without the powder.

[0020] Japanese Patent Application Laid-Open (Kohyo) No.11-507085discloses a flexible copolymer coating which can be bonded firmly to thesurface of a rubber article and extend without separation from thebonded surface. The patent, taking into consideration the removalproperty from the dipping former and the dry and wet wearing property,discloses an emulsion type copolymer between a reactive, low surfaceenergy monomer, preferably a silicone oligomer, and an alkyl acrylateand a reactive hard monomer.

[0021] There are many disclosures on the method for preparing the powderfree gloves by coating a hydrophilic hydrogel forming polymer on therubber surface and curing the polymer layer. The examples thereof areU.S. Pat. Nos. 3,326,742; 3,585,103; 3,607,473; 3,745,042; 3,901,755;3,925,138; 3,930,076; 3,940,533; 3,966,530; 4,024,317; 4,110,495; and4,125,477.

[0022] Further, U.S. Pat. No. 4,499,154 discloses a method ofmanufacturing a talc-free product by immersing a dipping former in anatural rubber latex, leaching the product in hot water, impregnatingthe product with a dilute acid, neutralizing the surface with water oran aqueous alkali solution, dipping in a hydrophilic hydrogel formablepolymer such as a copolymer of 2-hydroxyethylmethacrylate andmethacrylic acid or 2-ethylhexylacrylate and a crosslinking agentthereof, heating the coat layer to fix to the rubber, vulcanizing therubber, removing the product from the dipping former, coating a siliconecontaining a surfactant, and providing heat. This method also disclosesthat the slipping property for wet hands is improved by crosslinking thecoat layer of the hydrogel polymer of the invention and thereafter bytreating with a cationic surfactant such as a long chain aliphaticamine. The patent also discloses that impregnating the rubber surfacewith an aluminum salt after acid treatment is preferable. This methodcan afford powder-free rubber products, but it includes many steps andraises the manufacturing costs excessively and it cannot be adopted forthe product which dislikes the contamination of silicone.

[0023] U.S. Pat. No. 4,575,476 discloses that the coat layer of aspecific 2 -oxyethyl methacrylate hydrogel polymer has a good slippingproperty for dry hands . Further, by treating the above-mentionedhydrogel coat layer with a surfactant, specially with a cationicsurfactant and a long chain aliphatic amine, the slipping property forwet hands is improved.

[0024] Furthermore, by treating with a silicone containing surfactant,the adhesiveness of the surface without the hydrogel coat is markedlyimproved.

[0025] U.S. Pat. No. 5,688,855 discloses that the hydrophilicity of asolid surface gives lubrication to the surface in the presence of water,and that a hydrophilic concentration gradient is automatically generatedwithin the coat layer by dissolving in one solvent a hydrogel formingpolymer component and a water-soluble polymer component that has a lowcompatibility with the above component, coating them on the surface of arubber product, and evaporating the solvent to cause phase separation ofthe two components.

[0026] Japanese Patent Application Laid-Open (Kokai) No.11-269708discloses gloves laminated with a lubricant layer of a rubber or resincontaining collagen on the inside surface of gloves provided with a baselayer of a rubber or polymer.

[0027] The defect of coating on the rubber surface is that layerseparation occurs when the rubber is extended.

[0028] U.S. Pat. No. 4,499,154 discloses reinforcing the adhesion of thecoat layer by undercoating an acid on the rubber surface.

[0029] W093/06996-A1 proposes using as a coat layer a polymer having arepeated structure of specific ether group and ester group.

[0030] U.S. Pat. No. 4,548,844 discloses an improvement of adhesionbetween a rubber layer and a hydrogel layer through acid treatment andalso discloses that, by undercoating an aluminum cation or a cation oftrivalence or more prior to the coating of the hydrogel polymer or byadding it to the hydrogel polymer, the adhesion of the rubber layer andthe hydrogel polymer is enhanced. It is presumed that this is caused bybonding of a hydroxy or carboxyl group in the hydrogel polymer to aprotein in the rubber latex.

[0031] Japanese Patent Application Laid-Open (Kokai) No.6-70942discloses a multilayer product comprising a first layer formed from anatural rubber, a second layer of a natural rubber, polyurethane,poly(acrylamide/acrylic acid) and polyethylene oxide, and a third layerof an acryl copolymer and fluorocarbon telomer resin. The product iswearable under dry or wet conditions without the powder.

[0032] Japanese Patent Application Laid-Open (Kokai) No.10-95867discloses production of powder-free medical gloves by coating alubricating composition comprising the first and second ingredients onthe surface of an elastomer product on the wearer's side with which theelastomer product is contacted. Here, the first composition comprises atleast one compound selected from the group consisting of acetylene diol,organosilicone, amino modified silicone, and cationic surfactant. Thesecond composition is at least one compound selected from the groupconsisting of cationic surface active agent, organosilicone,amino-modified silicone and acetylene diol.

[0033] Japanese Patent Publication (Kokoku) No.7-4405 discloses a methodof treating a surface with a modified polysiloxane.

[0034] The methods for manufacturing rubber products containing nodusting powder includes the method in which a bivalent coagulant metalsalt such as calcium nitrate and a latex stabilized by adding a watersoluble surfactant stable against the said metal salt, preferably anonionic surfactant, or a resin polymer are brought into co-existence ina coagulation liquid, and the former coated with the said coagulant isdipped in the latex to coat the one side of the rubber product. Althoughthis method fails to make the rubber product substantially non-adhesive,it is possible to make the rubber product non-adhesive by adding apeeling or anti-adhesion agent to such coagulant composition as thethird component.

[0035] U.S. Pat. Nos. 3,286,011 and 3,411,982 to Kavalir et al. disclosesuch technology above mentioned. The patent, however, fails to make theproduct powder-free because it adopts the powder as the peeling agent.

[0036] The patent discloses that polyvalent metal salts like calcium,magnesium and aluminum can be used as the latex coagulants.

[0037] The above-mentioned U.S. Pat. No. 4,310,928 discloses a method offabricating surgery gloves which can be removed from a dipping former bydispersing a lipophilic substance into a coagulant liquid such ascalcium nitrate by using such a coagulant.

[0038] Japanese Patent Application Laid-Open (Kohyo) No.10-508899discloses a method for producing a rubber article freed from the powderby adding to the coagulant, an acrylic emulsion copolymer coatingcomposition and a silicone emulsion. The said coating composition ismade by copolymerization of a reactive silicone acrylate, an alkylacrylate and a hard monomer, but such a composition is a knownsubstance. The patent clarifies that the release becomes easy only whenthe silicone emulsion is added to the composition and that the glovesshows excellent dry-type and wet-type wearing performance.

[0039] EP 640,623 discloses a coagulant for natural rubber comprising asalt-stable polychloroprene or polyurethane and a bivalent metal saltand to that powder-free rubber gloves can be manufactured by furtheradding in the coagulant a peeling agent consisting of a polyethylene waxemulsion and a cationic surfactant.

[0040] In Japanese Patent Application Laid-Open (Kokai) No.11-236466surfactants and various waxes such as polypropylene wax emulsion inplace of the polyethylene wax emulsion were employed as adhesioneliminating agent or releasing agent, wherein the cationic surfactantfunctions for stabilizing the polychloroprene added to the coagulant andfunctions as a release agent between the polychloroprene and the dippingformer because the affinity for the dipping former is higher than thatfor the pertinent polymer.

[0041] Japanese Patent Publication (Kokoku) No.2-42082 discloses acoagulant composition formed by adding a latex, a surfactant or bivalentor trivalent metal salt into water.

[0042] In Japanese Patent Application Laid-Open (Kohyo) No.9-511708 theTeague method is adopted to the manufacture of polyurethane coatedgloves. Namely, a first layer is formed by dipping in an aqueousdispersion liquid or emulsion of a polyurethane polymer or copolymer,and the first layer is dipped in a coagulant then a latex compound toform a second layer. This literature also discloses a method of forminga lubricating polymer layer on the second layer.

[0043] There is disclosed technology regarding to powder-free gloveswhich use novel raw materials.

[0044] U.S. Pat. No. 5,851,683 proposes a special successivecopolymerization polymer as to powder-free gloves comprising athermoplastic elastomer for clean room.

[0045] As mentioned above, the method of preventing the adhesion ofemulsion/latex products is important in both sides of manufacture anduse of the products. Although various proposals have appeared, many ofsuch technologies are considerably complicated and such a method that issimple, effective and economical has not been developed. One reason forthis is that, since the main material is a natural rubber latex, anatural substance having strong adhesion and complicated causes for theadhesion, the treatment materials and techniques for the adhesionprevention possibly become complex.

[0046] The present invention, taking into consideration theabove-mentioned current status of adhesion treating technology, is toprovide a novel powder-free, non-adhesive carboxylated latex product andto a novel method of manufacturing the same. Further, the presentinvention provides a latex product having excellent durability in wearwithout sulfur vulcanization.

[0047] Disclosure of the Invention

[0048] We studied intensively to solve the above-mentioned problems, andhow found that the adhesion of the surface is strong if the surface of acarboxxylated latex product is not sufficiently crosslinked with abivalent metal compound as a coagulant and further that, even ifsufficient crosslinking is conducted with a mono- or bi-valent metalcompound, non-adhesion is insufficient since heating causes the adhesionbetween the inner and outer surfaces of the latex product. Assuming thatthe cause of the adhesion of a carboxylated latex product may lie inthat the carboxyl group of the latex forms a hydrogen bond throughwater, we studied methods to inhibit this hydrogen bond formation.

[0049] We first studied use of a metal compound having tri- or morevalence as an external crosslinking agent. For example, an aluminum saltwhich is a representative trivalent metal cation possesses very strongcoagulating ability according to the Shultz-Hardy Law but when onlyaluminum compound is used as the external coagulant for the purpose ofmaking a dipped product only the extremely thin film is formed. However,we found that a dip film having a usual thickness is formed by forming alayer of an external crossliking agent of aluminum compound on a dippingformer followed by forming thereon a coagulant layer of a usually usedmono- or bi-valent metal salt then dipping into the latex solution andfurther found that aluminum compound crosslinking layer is formed in theinnermost layer. Further surprisingly, it was found that the insidesurface of the dip film crosslinked with the aluminum compound isnon-adhesive and that bringing each of the inside surfaces into closecontact followed by heating under wet conditions does not cause theadhesion of each.

[0050] On the other hand, when the external crosslinking agent layer ofthe aluminum compound is formed on the external coagulant layer of mono-or bi-valent metal salt and subsequently dipped into the latex solution,only a thin film is formed. However, when external crosslinking agentlayer is formed on the external coagulant layer comprises a mixture ofthe mono- or bi-valent metal salt and the aluminum compound followed bydipping in the latex solution, surprisingly a film having usualthickness and non-adhesive inside surface is formed.

[0051] Next, we studied on making the outside surface of the dip filmnon-adhesive. A film was shaped by forming the external coagulant layeron the dipping former and dipping it into the latex. The film wasfurther dipped into the aluminum compound solution according to theusual method, followed by heating, thereby forming any aluminum compoundcrosslinking layer on the outside surface of the film. The outsidesurface of the film was non-adhesive. Further, after releasing the dipproduct from the dipping former, the both surfaces were dipped in thealuminum compound solution and subjected to subsequent heating. The bothsurfaces were found non-adhesive.

[0052] Based on the above-mentioned findings, the crosslinking layerformation reaction of the latex surface was tested using variouscompounds of metal elements having three or more valences, and it wasfound to be possible to produce a latex article having non-adhesivesurface.

[0053] Furthermore, we tested for surface treatment of the latex basesubstance with various organic crosslinking agents that crosslink thecarboxy group of the carboxylated latex in the same manner as with themetal compound having three or more valences. As the result, it wasconfirmed that the organic crosslinking agent gave non-adhesive latexproducts as with the tri- or more valent metal compound. Emulsion typecrosslinking agents tended to give high effect, and, even if consideredas the crosslinking agents of the same type, water soluble organiccrosslinking agents showed low effect. Moreover, the latex film formedby the dipping method by adding the water-soluble crosslinking agent tothe coagulant raised problems that cracks developed, the film strengthwas poor and so forth. Presumably, the crosslinking agent diffused intothe inside of the film to cause the so-called over-vulcanization, whichbrought forth the deterioration of strength.

[0054] We tested for addition of chemicals having coagulating effect tothe emulsion latex in order to prevent the diffusion of the crosslinkingagent, and confirmed that the undermentioned internal addition-usealuminum type inorganic crosslinking agents such as aluminates andaluminum hydroxide gels could be added to the emulsion latex withoutcoagulating the carboxylated latex. In addition, the latex film that wasnot made non-adhesive in the treatment with a concentration as high as1% of a water-soluble crosslinking agent such as oxazoline crosslinkingagent, e.g. Epocross W (made by Nippon Shokubai) , was made non-adhesivewhen such a compound having coagulation effect was added even in aconcentration as extremely low as 10 ppm.

[0055] As to the system in which the internal addition-use aluminum typeinorganic crosslinking agent such as aluminate or aluminum hydroxide gelwas added to an emulsion latex, the effect of the diffusion of organiccrosslinking agents was studied further. After forming a film with thecoagulant containing organic crosslinking agent, the effect on the filmstrength of the temperature of the leaching stage was examined. As aresult, the film strength lowered in the usual leaching stagetemperature of 50 to 60° C., but the decrease of the film strength wasnot observed when the treatment of the leaching stage was conducted at70° C. or more. Presumably, unlike the tri- or more valent metalcompound in the coagulation liquid, the crosslinking agent in theaqueous treatment solution, being poorly reactive with the carboxylgroup in the latex at a low temperature, diffuses toward the Z-axisdirection without staying on the surface of the latex product to causethe deterioration of the strength.

[0056] With the concentration of the organic crosslinking agentdecreased, its effect on the adhesion and strength of the latex productwas examined. Even with a concentration of the organic crosslinkingagent as extremely low as 0.001% (2×10⁻⁴ part per latex solids), thelatex product showed non-adhesion, and the strength of the product wasequivalent with that of the untreated product. The effect of the organiccrosslinking agents on the strength differs according to the propertiesthereof. Those which have a lower degree for the diffusion to the Z-axisdirection, or those which react immediately on the surface of the latexand do not diffuse into the inside exert less influence on the productstrength.

[0057] On the other hand, we conducted a wearing test for fingerstallsprepared in the test. The fingerstall obtained by vulcanizing thecarboxylated latex with zinc oxide, although showing good results in thestrength test, was found to be very poor in durability since the filmdeveloped cracks on wear from several hours to within one day. This isbecause the defect of ion crosslinking surfaced up.

[0058] We conducted a wearing test for the above-mentioned fingerstallswhich were obtained by adding an internally added aluminum typeinorganic crosslinking agent such as aluminate or aluminum hydroxide gelto an emulsion latex. Unexpectedly, they did not break when worn for aperiod from one day to one week. This is thought to be because, when theion crosslinking by zinc oxide cleaves on use, the aluminum ionretaining crosslinking power repairs the cleaved points. Thus, by addingthe internally added aluminum type inorganic crosslinking agent such asaluminate or aluminum hydroxide gel into the carboxylated latex, thenon-adhesion treatment becomes possible even with an extremely lowconcentration of the organic crosslinking agent that hitherto has beenincapable of non-adhesion treatment. Further, it becomes possible toproduce latex products excellent in durability without sulfurvulcanization.

[0059] The retesting on tri- or more valent metal compound crosslinkingagents gave similar results.

[0060] Other organic crosslinking agents for carboxyl group make thecarboxylated latex product non-adhesive at a lower concentration, as inthe said oxazoline type crosslinking agents.

[0061] Organic compounds which are not crosslinking agents for carboxylgroup but are considered to react with carboxyl group have similareffects. Such compounds include glyoxal, polyamide compound, polyamidepolyurea compound, polyamide polyureaglyoxal condensation reactionproduct, polyamine polyurea compound, polyamideamine polyurea compound,polyamideamine compound, polyamideamine epihalohydrine condensationreaction product, polyamideamine formaldehyde condensation reactionproduct, polyamine epihalohydrine condensation reaction product,polyamine formaldehyde condensation reaction product, polyamide poltureaepihalohydrine condensation reaction product, polyamide polyureaformaldehyde condensation reaction product, polyamine polyureaepihalohydrine condensation reaction product, polyamine polyureaformaldehyde condensation reaction product, polyamideamine polyureaepihalohydrine condensation reaction product, and polyamideaminepolyurea formaldehyde condensation reaction product. These compoundshave been developed as waterproof endowing agent, sizing agent,printability improver, wet strength enhancing agent, and paper strengthreinforcing agent of papers, and are common in that any of them is achemical for controlling hydrogen bonds in the paper.

[0062] Next, we studied compounds such as monofunctional epoxy compoundsand monofunctional amines that do not crosslink with the carboxyl groupof the latex but react with the carboxyl group to inhibit the formationof hydrogen bond derived from the carboxyl group.

[0063] As a result, it was confirmed that these compounds, which areconsidered to bond to a carboxyl group to lead to hydrophobicity, affordsimilar effects to those of the before-mentioned compounds.

[0064] We studied on sizing agents used in the field of paper aschemical to block carboxyl groups. The typical example of the sizingagent is the rosin type, and the main ingredient of rosin is abieticacid. The rosin coats pulp fibers and exhibits excellent hydrophobicityat that time. The contact angle of rosin and water is as large as 53°,and if aluminum is bonded the contact angle becomes as extremely largeas 130°. Thus, the rosin gives a large effect as hydrophobicity endowingagent. The rosin sizing agent wastested in the same manner as theabove-mentioned, and the effect as a blocking agent of carboxyl groupwas confirmed. The effect of the sizing agent is thought because itcoats the latex surface physico-chemically or physically intohydrophobicity, and it is estimated that aluminum ion plays a big role.

[0065] Further, in recent years, as the sizing agent for neutral paperthere are used alkylketenedimer(AKD), alkenylsuccinic acidanhydride(ASA), cationic sizing agent, and the like. These neutralsizing agents also had a similar effect. Regarding the hydrophobicityeffect of AKD and ASA, it is said generally that they createhydrophobicity by chemically bonding to a hydrophilic group. But, thereis a view that they cause autolysis on the surface of fiber to losehydrophilicity and the whole compound becomes hydrophobic. In this time,the hydrophilic group works as anchor. In any event, it is evident thatthe relevant sizing agent blocks the carboxyl group on latex surfacechemically, physico-chemically or physically to generate hydrophobicity.

[0066] We also studied on making the surface of latex productshydrophobic chemically or physically, taking the above-mentionedhydrophobicity effect into consideration. First, we had an eye to thehydrophobic group of surfactants and examined on nonionic surfactants.As the results, it was found that HLB, an index of hydrophilicity andhydrophobicity, could not interpret the degree of non-adhesion. Further,cationic and amphoteric surfactants do not have even such an index. Wethought it convenient to determine the propriety by conducting adhesiontest 1 or 2 as shown in the below-mentioned examples. The surfactantthat showed non-adhesion effect is called hereinafter a non-adhesivesurfactant.

[0067] The anionic surfactant has a similar effect as the saidsurfactant. However, the anionic surfactant loses the function ofsurfactant as soon as it forms a metal soap with polyvalent metal saltsderived from a coagulant. Many of the metal salts of the anionicsurfactants have adhesiveness, and the treatment with an anionicsurfactant sometimes gives an adverse effect. To grasp thecharacteristics of the compound itself, it is necessary to conduct theadhesion test.

[0068] For the surfactant to exhibit the non-adhesion effect, it isnecessary to add an internally added aluminum type inorganiccrosslinking agent such as aluminate or hydroxyaluminum gel directlyinto an emulsion latex.

[0069] We further studied, based on the above-mentioned findings, themethod of directly adding a carboxyl-group blocking agent into acarboxylated latex. When an article is made by the dipping method, thelatex film after the dipping is extracted with hot water on the leachingstage. Accordingly, the carboxyl-group blocking agent incorporated inthe latex liquates out on the leaching stage to fail in making thecarboxylated latex product non-adhesive. On the other hand, when thecarboxyl-group blocking agent is an emulsion type, when it reacts with acarboxylated emulsion latex, or when it is adsorbed on a carboxylatedemulsion latex, it reacts with a bivalent metal salt, preferably calciumsalt, in the coagulant and it dose not liquate out. In case where thereis a special condition that the caboxyl group blocking agent does notliquate out, for example, a condition that the calcium soap formed abovehas non-adhesion effect or a condition that the carboxyl-group blockingagent does not liquate out by reacting with the aluminum type inorganiccrosslinking agent such as aluminate or aluminumhydroxide gel added inthe carboxylated emulsion latex, only incorporating the carboxyl-groupblocking agent into the carboxylated emulsion latex gives a non-adhesiveproduct.

[0070] We also studied earnestly techniques for making carboxylatedlatex products non-adhesive through chlorination. Chlorination, whereinchlorine adds to the double bonds of rubber molecules on the bothsurfaces, outside and inside, of carboxylated latex products, produces,so to call it, a coat layer of chlorinated hydrocarbon, though it posesproblems regarding environmental measures.

[0071] For this reason the both surfaces of the rubber products lose therubbery properties, presenting hydrophobicity and non-adhesion. Thereare many problems in view of the manufacture which derive from thequality of chlorination, and a big problem in the manufacturing processis that on-machine chlorination on the both sides, with an article to bechlorinated being attached to a former, is not possible. Usually thechlorination is conducted on a separate step after the product has beenremoved from the former, or conducted on a separate step, afteron-machine chlorination of only the outside surface, with the productremoved from the former and with its inside surface reversed outwardly.This inevitably deteriorates production efficiency.

[0072] We have found the problem can be solved by a method whereinprovision of non-adhesion to the outside surface is carrying out byon-machine chlorination and provision of non-adhesion to the insidesurface is carried out by adopting a non-adhesion providing techniqueseparately invented by us (JP Application No. 2000-139733).

[0073] The techniques for providing non-adhesion to carboxylated latexproducts have been mentioned above. By chlorinating the outside surfaceof the carboxylated latex products which had been manufactured by usingsuch techniques, it was possible to produce non-adhesive carboxylatedlatex products. In case that the products are rubber gloves, they areturn inside out when they are removed from the former. Consequently, theinside surface has been subjected to chlorination, and gloves that aregood in wearing and removing properties are fabricated.

[0074] The carboxylated latex film which has been through withnon-adhesion measures as to the inside surface can be on-machinechlorinated by dipping into a chlorine aqueous solution or by contactingthe outside surface with chlorine gas. The outside surface of thechlorinated carboxylated latex products is non-adhesive, and the insidesurface thereof is non-adhesive through the non-adhesion providingtreatment.

[0075] Further, in the case of gloves, they are turn inside out whenpeeled off from the former, and the inside surface corresponds to thesurface that has undergone the chlorination. For this reason, wearingand removing the gloves are easy. As used herein, the outside surface inthe present invention means a face that does not contact with the formerin the dipping process, and the inside surface means one that contactswith the former.

[0076] The chlorination of the outside surface can be effected by aknown method.

[0077] That is, such methods can be adopted in which a formedcarboxylated latex film is dipped in a chlorine aqueous solution or putinto direct contact with chlorine gas. Since only one side is to bechlorinated, it can be performed by means of on-machine.

[0078] As mentioned above, it is possible by using the present inventionto fabricate the latex product which is non-adhesive in one or bothsurfaces thereof. The surfaces of such products do not attach togethereven when each surface comes in contact under heating during and afterthe manufacture of them. Accordingly, a product can be produced that hasnever existed until now.

[0079] One of such products is a non-adhesive fingerstall mechanicallywound on-machine from its mouth before removing from the dipping former.The fingerstall wound from the mouth has been existed until now, and itsusefulness has been recognized because of its easy to wear. However, theboth surfaces of the fingerstall, a latex product, are intrinsicallyadhesive, and in order to manufacture the wound product, the fingerstallhad previously to be made non-adhesive by a treatment such as powderingand post-chlorination, followed by winding with human hands. This madeit impossible to maintain the cleanness of the product in a high leveland it was difficult to use such a product in a workplace whereprecisely processed articles are manufactured. In contract, the presentinvention, which is able to make the both surfaces of a formed latexnon-adhesive, can provide a method to mecahnically wind a fingerstall ona dipping former and can maintain the cleanness of the product to a highdegree. Recently, a thin fingerstall is desired since wearing a thickone tends to cause tiredness. The thinner the fingerstall the moredifficult to wear it, so desired is a wound fingerstall that is thin,powder-free, non-adhesive and clean. By utilizing the property that theboth surfaces of the fingerstall are non-adhesive, a fingerstall withwound mouth can easily be manufactured. In manufacturing thefingerstall, the top of the stall is left adhesive without providing thelayer of carboxyl-group blocking agent, the whole is wound up, and thenunwound. By this, the adhesive portion remains as wound mouth. Hitherto,the wound mouth has been formed first by winding up only the top of thestall to make the wound mouth, and thereafter the stall must have beenreleased from the former in another step. The wound mouth facilitateswear and removal of the stall and is highly desired for flat products.Further, after formation of the wound mouth by the conventional method,a non-adhesion treatment may be conducted. This procedure is alsoapplicable to the wound fingerstall described in the precedingparagraph, thereby providing the fingerstall with wound mouth.

[0080] The present invention relates to:

[0081] (1) A non-adhesive carboxylated latex product incorporated with acarboxyl-group blocking agent,

[0082] (2) A non-adhesive carboxylated latex product having a layertreated with a carboxyl-group blocking agent on one or both surfaces ofa carboxylated latex product or a carboxylated latex productincorporated with a carboxyl group blocking agent,

[0083] (3) A non-adhesive carboxylated latex product having a layertreated with a carboxyl group blocking agent on the inside surface of acarboxylated latex product or a carboxylated latex product incorporatedwith a carboxyl group blocking agent and having a chlorination treatmenton the outside surface.

[0084] (4) A non-adhesive carboxylated latex product according to (1) to(3), wherein the carboxylated latex is NBR, SBR, CR or MBR, (5)Adurable, non-adhesive carboxylated latex product according to (1) to(4), wherein the carboxylated latex is added and crosslinked with aninternally added aluminum-type inorganic crosslinking agent,

[0085] (6) A non-adhesive carboxylated latex product according to (1) to(5) wherein the latex product is a dip product,

[0086] (7) A non-adhesive carboxylated latex product according to (6),wherein the dip product is a fingerstall, gloves, balloon or condom,

[0087] (8) A non-adhesive carboxylated latex product according to (1) to(7), wherein the carboxyl-group blocking agent is a metal elementcrosslinking agent having three or more valences,

[0088] (9) A non-adhesive carboxylated latex product according to (8),wherein the metal element crosslinking agent having three or morevalences includes at least one selected from aluminum, titanium orzirconium compounds,

[0089] (10) A non-adhesive carboxylated latex product according to (1)to (7), wherein the carboxyl-group blocking agent is an organiccrosslinking agent for the carboxyl group of the carboxylated latex,

[0090] (11) A non-adhesive carboxylated latex product according to (10),wherein the organic crosslinking agent for the carboxyl group includesat least one selected from aziridine compounds, epoxy componds, blockedisocyanates, oxazoline compounds, carbodiimido compounds,melamineformaldehyde resins, ureaformaldehyde resins, isocyanates,phenolformaldehyde resins, glycols, polyols, diamines, polyamines,hexamethoxymethylmelamines and methylolacrylamides,

[0091] (12) A non-adhesive carboxylated latex product according to (1)to (7), wherein the carboxyl-group blocking agent includes at least oneselected from glyoxals, polyamide compounds, polyamide polyureacompounds, polyamine polyurea compounds, polyamideamine polyureacompounds, polyamide polyurea glyoxal reaction products, polyamideaminecompounds, polyamideamine epihalohydrine condensation reaction products,polyamideamine formaldehyde condensation reaction products, polyamineepihalohydrine condensation reaction products, polyamine formaldehydecondensation reaction products, polyamidepolyurea epihalohydrinecondensation reaction products, polyamide polyurea formaldehydecondensation reaction products, polyamine polyurea epihalohydrinecondensation reaction products, polyamine polyurea formaldehydecondensation reaction products, polyamideamine polyurea epihalohydrinecondensation reaction products, and polyamideamine polyurea formaldehydecondensation reaction products,

[0092] (13) A non-adhesive carboxylated latex product according to (1)to (7), wherein the carboxyl-group blocking agent includes at least oneselected from monofunctional amines, monofunctional epoxy compounds,monofunctional isocyanates and monofunctional blocked isocyanates,

[0093] (14) A non-adhesive carboxylated latex product according to (1)to (7), wherein the carboxyl-group blocking agent is a sizing agent,

[0094] (15) A non-adhesive carboxylated latex product according to (1)to (7), wherein the carboxyl-group blocking agent is a non-adhesionsurfactant,

[0095] (16) A method for producing a non-adhesive carboxylated latexproduct according to (1) to (15), wherein one or both surfaces of thelatex product are brought into contact with one or more of thecarboxyl-group blocking agent solutions described in (8) to (15) toattach the carboxyl-group blocking agent to the latex surface,

[0096] (17) A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that there is used a solution of a mono- orbi-valent external coagulant for carboxylated latex which is mixed withor dissolved in one or more of the carboxyl group blocking agentsdescribed in (8) to (15),

[0097] (18) A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that a dipping former is dipped and depositedwith one or more of the carboxyl-group blocking agent described in (8)to (15), dipped and deposited with a mono- or bi-valent externalcoagulant, and then dipped in a latex,

[0098] (19) A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that a dipping former is dipped and depositedwith one or more of the carboxyl-group blocking agents described (8) to(15), then dipped in a latex liquid to form a latex film, further dippedin a mono- or bi-valent external coagulant solution, and subsequentlydipped in the carboxylated latex again,

[0099] (20) A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that a dipping former is dipped in a mixtureof one or more of the carboxyl-group blocking agents described in (8) to(15) and a carboxylated latex stable to the blocking agent to form alatex film, further dipped in a mono- or bi-valent external coagulantsolution, and thereafter dipped in the carboxylated latex again,

[0100] (21) A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that a dipping former is dipped in a mono- orbi-valent coagulant suspension for carboxylated latex which contains, asthe carrier, fine powder of one or more of the carboxyl group blockingagents described in (8) to (15) that is hardly soluble or insoluble inwater or alcohol, and subsequently dipped in the carboxylated latexliquid.

[0101] (22) A non-adhesive fingerstall, wherein the fingerstalldescribed in (7) has a shape mechanically wound from the mouth beforeremoved from the dipping former,

[0102] (23) A non-adhesive fingerstall according to (7) or (22) whichhas a wound mouth,

[0103] (24) A method for producing a non-adhesive fingerstall with woundmouth according to (23), characterized in that an adhesive portion isprovided on the upper part at the time of dipping and then winding isconducted,

[0104] (25) A method for producing a non-adhesive fingerstall accordingto (7) or (22), characterized in that the outside surface is treatedwith a carboxyl group blocking agent after a wound mouth is provided.

[0105] The term carboxyl group blocking agent as used herein means asubstance which blocks a carboxyl group chemically, physico-chemicallyor physically and inhibits the formation of a hydrogen bond derived fromthe carboxyl group. Specifically, it means a compound which can make thecarboxylated latex non-adhesive in the adhesion test 1 or 2 of theexamples. Further, the non-adhesion surfactant refers to a surfactantwhich can make the carboxylated latex non-adhesive in the adhesion test1 or 2.

BRIEF DESCRIPTION OF THE DRAWINGS

[0106]FIG. 1 is a perspective view of the dipping former transferringapparatus used in the examples. 1, chain; 2, guide rail; 3, dippingformer; 4, rod; and 5, guide.

[0107]FIG. 2 shows the trial apparatus for manufacturing the fingerstallused in the examples. 6, dipping tank; 7, drying furnace; 8, windingmachine; and 9, unwinding machine.

[0108]FIG. 3 shows the main parts of the winding machine. 10, rollingbrush; and 11, film.

[0109]FIG. 4 shows the main parts of the unwinding machine.

BEST MODE FOR CARRYING OUT THE INVENTION

[0110] The present invention is described in more detail hereinafter.The first non-adhesive carboxylated latex product of the invention is alatex product in which non-adhesiveness properties have been afforded bydirectly adding a carboxyl group blocking agent into an emulsion latex.

[0111] The second is a carboxylated latex product having a treatmentlayer of the carboxyl group blocking agent on one or both surfaces ofthe carboxylated latex base. Both products are intrisicallynon-adhesive. If special use characteristics such as dry or wet wearingproperties are required, an outer layer can be provided further on theoutside surface according to known technology. The latex products whichneed prevention against adhesion include, but are not limited to, dipproducts such as balloons, gloves, fingerstalls and condoms, extrudedproducts such as rubber threads and rubber pipes, cast-molded productssuch as balloons and toys, and whole rubber products or products havingrubber surface such as rubber sheets, hoses and draw clothes.

[0112] The kind of the carboxylated latex used herein is not limited,but among elastomer latexes of NBR, SBR, CR, MBR and the like, onessubjected to carboxylation are preferable.

[0113] There is no limitation about a so-called vulcanizing agent addedto the carboxylated latex, and normal vulcanizing agents can be used:e.g., agents for sulfur, peroxide, zinc oxide or radiationvulcanization. However, when the latex product is used in the fieldwhere the reaction of a metal and sulfur is undesirable, for example inthe field of precision instrument, sulfur cannot be used as avulcanizing agent. For such use the product vulcanized by zinc oxide isgenerally used, but there is a risk that it may break during wearbecause of ion crosslinking. Especially for thin gloves or fingerstallsdurability is required. By adding an internally added aluminum typeinorganic crosslinking agent into the carboxylated latex, durability isgreatly improved. At the same time, the range of compounds that canfunction as carboxyl group blocking agent becomes sharply wide and theamount to be added can sharply be decreased. Here, the internally addedaluminum type inorganic crosslinking agent refers to an inorganicaluminum compound which do not coagulate the latex at ordinarytemperature even when directly added to the carboxylated latex and whichcrosslinks the carboxylated latex when heated. The typical examplesthereof are alkali metal aluminates such as water-soluble sodiumaluminate, alkaline earth metal aluminates such as sparingly solublecalcium aluminate, and aluminum hydroxide gel.

[0114] Also included are the groups of various aluminum compounds suchas magnesium aluminate metasilicate, synthetic hydrotalcite,aluminosilicagel and aluminosilicate. In other words, they are compoundswhich do not dissociate into aluminum ion when added but combine with acarboxyl group of the latex through ionic crosslink when heated. Thealuminum-ion crosslink of these compounds is considered to occur viaaluminum hydroxide.

[0115] When the latex product is a dip product, it is preferable to usean external coagulant, and any of the usually used external coagulantcan be employed. Usually, mono- or bi-valent metal salts are used, andthe monovalent salts include ammonium salts. Here, the externalcoagulant means one that is not directly incorporated into the latex butused in the coagulation-dipping process including depositon to thedipping former.

[0116] The carboxyl group blocking agent used in the invention is acompound which acts on-a carboxyl group of the carboxylated latexchemically, physico-chemically or physically, thereby resulting inhydrophobicity which inhibits the formation of a hydrogen bond derivedfrom the carboxyl group so as to make the latex product non-adhesive.

[0117] The first carboxyl group blocking agent is a tri-or more valentmetal compound. Although any agent can be used if it has three or morevalences, it is necessary to fully consider safety and side effect(discoloration) of the compound.

[0118] The example of the tri- or more valent metal compound usable asthe external crosslinking agent in the invention includes one which issoluble in water or alcohol and one which is sparingly soluble orinsoluble. The soluble trivalent metal compound includes aluminum salts,ferric salts, chromate and thorium salts. Practically, suitable arealuminum salts such as aluminum chloride, aluminum nitrate, aluminumsulfate and aluminum acetate.

[0119] Polyaluminumchloride(PAC) and water-soluble polyaluminumhydroxide are more preferable because they have three or more valences.Especially, water-soluble polyaluminumhydroxide gives the effect at itslow concentration comparable to that of the organic crosslinking agent,as shown in the examples. If the metal is an amphoteric element, itsmetal acid salt is usable and sodium aluminate is a typical example.Observation suggests that sodium aluminate is converted into aluminumhydroxide on the film latex surface and then causes crosslinking.

[0120] The metal compound sparingly soluble or insoluble in water oralcohol that acts as the external crosslinking agent includes oxides,hydroxides and alkaline earth metal salts. The typical examples arealuminum hydroxide, calcium aluminate and magnesium aluminate. Thealuminum compound includes various substances such as aluminosilicates,which fall into the invention. The usual crystalline aluminum hydroxideis hardly involved in the crosslinking reaction. The so-called amorphousaluminum hydroxide, when dispersed with a ball mill and made to have alarge specific surface, is involved in the crosslinking reaction, and isabsorbed on the latex film surface formed. Further, calcium aluminateand magnesium aluminate are absorbed on the latex surface in the sameway.

[0121] As used herein, the external crosslinking agent refers to the onethat is not directly incorporated into the based emulsion latex andcrosslinks the latex by contacting with the surface of the emulsionlatex or latex film.

[0122] The tetravalent metal compound used in the invention includeszirconium compounds such as zirconyl nitrate, ammonium, zirconylcarbonate zirconyl carbonate W, ammonium carbonate zirconuimoxychloride, and titanium compounds such as titanium lactate, titaniummaleaic anhydride and titanium oxalate.

[0123] In the case of a tri- or more valent water soluble metal salt,the dissociated metal ion is cationic and reacts with the anion ofcarboxyl group even at low temperature. Further, according to theShultz-Hardy Law, it has a strong crosslinking force. Because of this,the difussion of the metal ion having three or more valences is veryweak, and the reduction of strength of the latex film is minimumized.Accordingly, the quality of the final product is kept favorable even ifthe concentration of the metal salt is considerably high.

[0124] The tri- or more valent metal compounds used in the inventioninclude organic compounds. The typical examples are carboxylic acidsalts, respectively the above-mentioned aluminum acetate, zirconiumacetate, titanium lactate, titanium maleic anhydride, titanium oxalateand titanium lactate. They are not limited to carboxylic acid salts.

[0125] The concentration of the tri- or more valent metal externalcrosslinking agent varies depending on the kind of latex, the amount offunctional groups involved in the reaction, the kind and quantity of anemulsifier or dispersant, the kind of a crosslinking agent, a treatmentmethod, and the crosslinking agent supporting ability of a dippingformer. Preferably, it is in the range of 0.1 to 5% (as metal oxidecorresponding to the metal element). When the agent is used byincorporation into the external coagulant, it exhibits a sufficienteffect in the range of 0.01 to 0.5%. In the case of working it on theformed latex film and in the case of providing the external coagulantlayer on the external crosslinking agent layer, a preferableconcentration is 0.2 to 1%. When the agent is used through incorporationinto the external coagulant, it replaces monovalent cations of thelatex, usually ammonium ion, potassium ion and sodium ion, to form acrosslink, whereas one other than the above is used as a coagulant andnecessary to be replaced with a bivalent cation, usually calcium ion,bonded to the latex to form a crosslink.

[0126] In the system in which the internally added aluminum typeinorganic crosslinking agent is directly added to the latex, theconcentration of the external crosslinking agent can be decreased.

[0127] The second carboxyl group blocking agent is an organiccrosslinking agent for the carboxyl group of the carboxylated emulsionlatex. Any kind is usable as long as it is an organic crosslinking agentcapable of crosslinking a carboxyl group. The typical organiccrosslinking agent usually used includes, but are not limited to,aziridine compound, epoxy compound, blocked isocyanate, oxazolinecompound, carboimide compound, melamineformaldehyde resin,ureaformaldehyde resin, isocyanate, phenolformaldehyde resin, glycol,polyol, diamine, polyamine, hexamethoxymethylmelamine andmethlolacrylamide. (see Newest Applied Technology of Latex Emulsion,page 323, Motoharu Okikura (ed) published by Chunichisha, Japan)

[0128] The organic crosslinking agent for carboxyl group reacts at aconsiderably high temperature. However, according to the invention,since its amount is very small, it shows the effect at a temperature ofabout 90 to 120° C. However, if time lapses on the stage of a lowtemperature, the crosslinking agent diffuses in the Z-axis directionbefore strength of the latex film is expressed, and competes with theso-called latex vulcanizer such as zinc oxide to restrain vulcanization,resulting in lowering the film strength. Particularly, the temperatureof the leaching stage of a dipping method is preferably 65° C. or more,more preferably 70 to 85° C. The temperature of 85° C. or more is notpreferable because bubbles are generated between the dipping former andthe film. When the concentration of the organic crosslinking agent inthe coagulant is high, diffusion of the crosslinking agent becomes largeand the strength is lowered. But, an emulsion type crosslinking agent orhighly reactive crosslinking agent diffuses weakly, and the degree ofthe diffusion also differs depending on the solubility of thecrosslinking agent in the coagulant solution. Therefore, it ispreferable to determine optimal conditions through an adhesion test. Analmost suitable concentration can be determined by carrying out the testat two levels of effective ingredient concentration, 0.025% and 0.0025%.The amount of a crosslinking agent to make the carboxylated emulsionlatex product non-adhesive is extremely small.

[0129] Organic compounds which do not belong to the crosslinking agentfor carboxyl group but are thought to react with a carboxyl group, alsohave the similar effect. As such effective compounds are the following:glyoxal, polyamide compound, polyamidepolyurea compound,polyamidepolyureaglyoxal condensation reaction product,polyaminepolyurea compound, polyamideaminepolyurea compound,polyamideamine compound, polyamideamineepihalohydrine condensationreaction product, polyamideamineformaldehyde condensation product,polyamineepihalohydrine condensation reaction product,polyamineformaldehyde condensation reaction product,polyamidepolyureaepihalohydrine condensation reaction product,polyamidepolyureaformaldehyde condensation reaction product,polyaminepolyureaepihalohydrine condensation reaction product,polyaminepolyureaformaldehyde condensation reaction product,polyamideaminepolyureaepihalohydrine condensation reaction product, andpolyamideaminepolyureaformaldehyde condensation reaction product.

[0130] Many of these compounds were developed as waterproof endowingagent, printability improver, wet strength improver, paper strengthreinforcing agent of papers, and they are common in that they weredeveloped as chemicals to inhibit the formation of hydrogen bonds inpaper. The reaction conditions and the concentration of the compoundsare similar to those of the organic crosslinking agent, providingcomparable effects.

[0131] The methods of producing the above-mentioned compounds are notlimited, but the general methods are described hereinafter.

[0132] The polyamide compound (also called polyamideamine compound) isobtained by dehydration condensation reaction of a polyamine and acompound having carboxyl group. The polyamidepolyurea,polyaminepolyurea, polyamideaminepolyurea and polyamideamine compoundsare reaction products between polyalkylenepolyamine oralkylenepolyamine, urea, and dibasic carboxylic acid. The compounds canbe modified with a small amount of aldehyde, epihalohydrine or α,λ-dihalo-β-hydrine. The method of their production is described inJapanese Patent Publication (Kokoku) No.59-32597 and Japanese PatentApplication Laid-Open (Kokai) No.4-10097.

[0133] The polyamideamine-epihalohydrine condensation reaction product,polyamideamine-formaldehyde condensation reaction product,polyamine-epihalohydrine condensation reaction product,polyamine-formaldehyde condensation reaction product,polyamidepolyurea-epihalohydrine condensation reaction product,polyamidepolyurea-formaldehyde condensation reaction product,polyaminepolyurea-epihalohydrine condensation reaction product,polyaminepolyurea-formaldehyde condensation reaction product,polyamideaminepolyurea-epihalohydrine condensation reaction product andpolyamideaminepolyurea-formaldehyde condensation reaction product, arereaction products between polyalkylenepolyamine, urea, dibasiccarboxylic acid, and epihalohydrine or formaldehyde. The manufacturemethods are described in Japanese Patent Publication (Kokoku)No.52-22982, Japanese Patent Publication (Kokoku) No.60-31948, JapanesePatent Publication (Kokoku) No.61-39435 and Japanese Patent ApplicationLaid-Open (Kokai) No.55-127423.

[0134] The sizing agent for paper is a chemical which makes thehydrophilic group of paper hydrophobic and prevents the soak of ink, andalso such chemical makes the carboxylated latex product non-adhesive. Itis considered that the chemical makes carboxyl group hydrophobicchemically, physico-chemically or physically. There is no establishedtheory for the hydrophobicity-forming mechanism, but the sizing agentgives a large and stable effect since it has been developed as a sizingagent of paper.

[0135] The sizing agent for paper includes internally added sizingagents and surface sizing agents. The invention can use any sizing agenton the like as long as it exhibit the function.

[0136] The internally added sizing agent is classified into an acidsizing agent, a neutral sizing agent and an acid/neutral sizing agent(Japanese Patent Application Laid-Open (Kokai) No.11-61682).

[0137] The acid sizing agent includes rosin sizing agent, fatty acidsoap sizing agent, synthetic sizing agent and petroleum resin sizingagent.

[0138] The rosin sizing agent includes rosins and rosin derivatives. Therosins refer to gum rosins, wood rosins and tol oil rosins whichcontain, as the main component, resin acids such as abietinic acid,palustric acid, neoabietinic acid, pimaric acid, isopimaric acid anddehydroabietinic acid.

[0139] The rosin derivatives include hydrogenated rosins, polymerizedrosins, modified rosins, fortified rosins, rosin esters and fortifiedrosin esters.

[0140] The modified rosins include (alkyl)phenol-formalin resin modifiedrosins, xylene resin modified rosins, aldehyde modified rosins andstyrene modified rosins.

[0141] The fortified rosins are obtained by heating and reacting thesaid rosins and α,β-unsaturated carboxylic acids.

[0142] The rosin esters are produced using rosins and polyhydricalcohols by the known esterification.

[0143] The fortified rosins are obtained by successively orsimultaneously reacting the said rosins and/or the said modified rosinswith known polyhydric alcohols and α,β-unsaturated carboxylic acids.

[0144] The fatty acid soap sizing agent is a sizing agent obtained byneutralizing a fatty acid having the carbon number of about 8 to 24 suchas palmitic acid or stearic acid and a mixture thereof with an alkali.

[0145] The synthetic sizing agent includes the sizing agent obtained byneutralizing with an alkali a substituted succinic anhydride obtained byreacting an oligomer, dimer or tetramer, of isobutene and a mixturethereof with maleic anhydride.

[0146] The petroleum resin sizing agent includes one obtained bymodifying a petroleum resin with an unsaturated carboxylic acid such asmaleic acid. The petroleum resin includes C5 petroleum resin obtained bypolymerizing C5 olefin such as 1,3-pentadiene or isoprene, C9 typepetroleum resin obtained by polymerizing C9 olefin such as coumarone orindene, C5/C9 copolymer type petroleum resin obtained by copolymerizingC5 olefin and C9 olefin, and dicyclopentadiene type petroleum resinobtained by polymerizing dicyclopentadiene or its derivative.

[0147] The neutral sizing agent includes alkylketenedimer type,alkenylketene dimer type, alkenyl succinic anhydride type and neutralrosin type sizing agents.

[0148] The alkylketene dimer type or alkenylketene dimer type sizingagent can be usually produced by emulsifying an alkylketene dimer oralkenylketene dimer which is prepared by treating a saturated orunsaturated fatty acid chloride having the carbon number of about 12 to24 with a base such as triethylamine to make a dimer.

[0149] The alkenyl succinic anhydride type sizing agent can be preparedby emulsifying an alkenyl succinic anhydride obtained by additionreaction of a terminal and/or internal olefin having the carbon numberof about 12 to 24 with maleic anhydride.

[0150] The neutral rosin sizing agent includes polyhydric alcohol estersof rosins, and emulsions made by dispersing petroleum resin-containingsubstances in water.

[0151] The polyhydric alcohol esters of said rosins include reactionproducts containing rosin esters obtained by reacting rosins, with (a)at least one chemical belonging to the scope of polyhydric alcohols and(b) at least one chemical belonging to the scope of α,β-unsaturatedcarboxylic acid or its derivative.

[0152] As the acid/neutral sizing agent there are known cationized fattyacid bisamide type, cationized petroleum resin type, cationized polymertype and α-hydroxycarboxylic acid type sizing agent.

[0153] The cationized fatty acid bisamide type and cationized petroleumresin type sizing agent are synthesized by reacting a maleic acid adductof a fatty acid having about 12 to 24 carbons or a petroleum resin witha polyamine such as diethylenetriamine and triethylenetetramine and amixture thereof, followed by reaction with epichlorohydrine.

[0154] The cationic polymer type sizing agent is usually synthesized byradical polymerizing a cationic vinyl monomer such asdimethylaminoethylmethacrylate and a hydrophobic monomer such asstyrene, acrylonitrile or alkyl(meth)acrylate in water and/or in anorganic solvent.

[0155] The α-hydroxycarboxylic acid type sizing agent is made byreacting a higher alcohol or higher amine with an oxyacid such as citricacid.

[0156] The surface sizing agent generally comprises a hydrophobicportion and an anionic portion such as carboxyl group. The surfacesizing agent is obtained by copolymerizing a hydrophobic monomer and ananionic monomer such as α,β-unsaturated monocarboxylic acid,α,β-unsaturated dicarboxylic acid and unsaturated sulfonic acid. (seeJapanese Patent Application Laying-Open (kokai) No.12-45197)

[0157] The example of the surface sizing agent which consists of acopolymer of a hydrophobic monomer and an anionic monomer includesstyrene-(meth)acrylic acid copolymer, styrene-(meth)acrylicacid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer,styrene-maleic acid-maleic acid halfester copolymer,(di)isobutylene-maleic acid copolymer, (di)isobutylene-maleicacid-maleic acid halfester copolymer and salts of these.

[0158] The surface sizing agent other than the above-mentioned includesalkylketene dimer, alkenyl succinic acid(anhydride), styrene-acrylicacid copolymer, acrylate-acrylonitrile copolymer,styrene-dialkylaminoalkyl (meth)acrylate copolymer, and reaction productthereof with epihalohydrine.

[0159] The carboxyl group blocking agent is not necessarily acrosslinking agent for carboxyl group. If it is a substance which actson carboxyl group chemically or physico-chemically further orphysically, which makes the site hydrophobic and hinders the formationof a hydrogen bond, the agent makes the carboxylated latex productnon-adhesive.

[0160] Concretely, even the compounds that cannot form crosslinkingstructure with carboxyl group, for example, monofunctional amines,monofunctional epoxy compounds, monofunctional isocyanates andmonofunctional blocked isocyanates, make the carboxylated emulsion latexproduct non-adhesive. Since they have one functional group, crosslinkingdoes not occur. However, if these compounds have hydrophobic group theyreact with a carboxyl group to result in hydrophobicity.

[0161] As to the amines, any of primary, secondary, tertiary andquarternary amines gives the effect.

[0162] The surfactant is composed of hydrophilic group and hydrophobicgroup.

[0163] If the hydrophilic group is arranged to the surface of thecarboxylated emulation latex product and the hydrophobic group to theoutside, supposedly the carboxyl group of the product surface is blockedto form hydrophobicity and to make the surface non-adhesive.Accordingly, it is supposed that the degree of hydrophobicity of thesurfactant controls the degree of non-adhesion of the product. Whetherthe surfactant takes up the position on the product surface with thehydrophobic group directed to the outside is determined by the physicaland chemical properties of the surfactant itself, the properties of thelatex, addition or no addition of aluminum compounds and the like. Andit is difficult to find a general rule. So, it is necessary to selectnon-adhesion surfactant through the adhesion test 2 shown in theexamples. The results of the test were that the surfactant showed thenon-adhesion effect in the case that the internal addition-use aluminumtype inorganic crosslinking agent such as aluminum hydroxide gel andaluminate was added into the emulsion latex. The presumable reason forthis is that the surfactant, viewed in the light of its properties,diffuses the latex film. The internal addition-use aluminum typeinorganic crosslinking agent is thought to suppress diffusion of thesurfactant.

[0164] Regarding to the nonionic surfactant, a general tendency cannotbe found. However, it is seen that the nonionic surfactant having a highHLB shows a lowered non-adhesion effect and that the nonionic surfactantof amine and amide types shows a high non-adhesion effect.

[0165] In the cationic surfactant and the amphoteric surfactant, thecation of the surfactant and the anion of the carboxyl group combinewith ion linkage. Hence, many of these give good results when subjectedto the above-mentioned adhesion test. However, since the bothsurfactants make chemical reaction with carboxyl group at lowtemperatures, they influence the formation of the latex film in thedipping step, if they are added in the coagulant for use. That is,according to the kind and concentration of the surfactant, fine wrinklesare generated toward the direction of the dipping, and sometimes cracksare generated. Further, if the surfactant diffuses into the inside, itcompetes with the so-called latex vulcanizing agent such as zinc oxideand hinders vulcanization to cause decrease of the strength.Consequently, countermeasures are needed of restraining the surfactantconcentration low to suppress diffusion, accelerating vulcanization byraising the temperature of the drying and leaching process and so forth,and these are big drawbacks. From the above-mentioned point the adhesiontest is needed.

[0166] It is unclear how the anionic surfactant gives the non-adhesioneffect. Generally, the anionic surfactant is used as an emulsifier insynthesizing the carboxylated emulsion latex. Moreover,dodecybenzenesulfonic acid, for example, reacts with metal salts in thecoagulant at the dipping, most of it being converted to metal soap, andit loses the function as surfactant. Metal soaps, as seen from the factthat they are used as lubricating oil, have more or less adhesion. But,among the anionic surfactants some show excellent non-adhesion effect.There are many effective surfactants among those that have amine andamide group in the structure and are considered to react with carboxylgroup and those that have a polycyclic structure and are considered tobe highly hydrophobic. For example, the use of naphthalenesulfonic acidformaline condensation reaction products or alkylnaphthalenesulfonicacid formaline condensation reaction products is effective. Theabove-mentioned rosin sizing agent is interpreted to belong to thiscategory.

[0167] The surfactant, because of its properties, has a great effect oneach manufacturing step of the carboxylated emulsion latex product andon the properties of the product. Therefore, in order to judge whether asurfactant is usable or not, it is necessary to confirm the non-adhesioneffect by conducting the adhesion test and at the same time to study theeffect on film forming and quality.

[0168] There are a variety of methods for manufacturing the non-adhesionlatex product of the invention.

[0169] When the product has already been formed into a film, it ispossible to bring one surface or both surfaces of the product in contactwith the carboxyl group blocking agent solution and to treat thecarboxylated latex surface with the said blocking agent. According tothe kind of the carboxyl group blocking agent, the reaction is veryfast, and at the time when the product is taken out, sometimes the latexfilm surface has already lost adhesiveness. But sometimes heating isneeded after the product has been taken out. Either way, to obtain thetreatment effect fully, it is desirable to conduct heat treatment.

[0170] In the case of a dip product, by depositing one or more carboxylgroup blocking agents and a usual external coagulant onto the dippingformer and then bringing into contact with the emulsion latex,coagulation of the latex and treatment with the blocking agent can beconducted at the same time.

[0171] There are four methods for depositing the carboxyl-group blockingagent on the dipping former. The first method is one wherein a usualexternal coagulant consisting of mono- or bi-valent metal salt and oneor more of the carboxyl group blocking agent of the invention are mixedand dissolved and deposited onto the dipping former. The second methodis one wherein the carboxyl-group blocking agent of the invention isdeposited onto the dipping former and thereafter a usual externalcoagulant is deposited onto the formed layer. Modifying this methodgives a method wherein the carboxyl group blocking agent is incorporatedinto the emulsion carboxylated latex, the dipping former is dipped insaid formulation liquid to form a thin latex film, the former is dippedin mono- or bivalent external coagulation solution, and then the formeris dipped in the carboxylated latex solution again.

[0172] The third method is one wherein one or more of the powderycarboxyl blocking agents of the invention is used as support, saidcarboxyl group blocking agent being suspended in a usual externalcoagulant solution, and then deposited onto the dipping former. Thismethod does not give a perfect non-powder product, but, since thecarboxyl-group blocking agent reacts with the latex and is absorbed, thepowder can be reduced to such a degree as unable to be perceived on thefinished product.

[0173] By immersing such dipping former in the emulsion latex, there isobtained a dip product in which the inside surface contacting the formeris non-adhesive.

[0174] The fourth method is one wherein a thin, carboxyl group blockingagent treated film of the latex is formed by using the carboxyl groupblocking agent as an external coagulant, the external coagulantconsisting of a mono- or bi-valent metal compound is deposited onto thefilm, and the former is dipped in the latex liquid again. With thismethod it is possible to make the inside surface non-adhesive, but it isfeared that peeling may occur between layers of the product.

[0175] Further, the outside surface can be made non-adhesive by theabove-mentioned methods.

[0176] In the case of cast-mold products, the inside surface of the moldis treated only with the carboxyl group blocking agent of the invention.

[0177] As mentioned above, it is possible by using the present inventionto fabricate the latex product non-adhesive in one or both surfaces. Thesurface of such products does not attach together when each surfacecomes into contact under heating during and after manufacturing them.

[0178] Accordingly, by utilizing such a property, a product can beproduced that has never existed until now.

[0179] One of such products is a non-adhesive fingerstall mechanicallywound from its mouth before removing from the dipping former. Thefingerstall wound from the mouth has been existed until now, and itsusefulness has been recognized because of its easy to wear. However, theboth surfaces of the fingerstall, a latex product, are intrinsicallyadhesive, and in order to manufacture the wound product, the fingerstallis previously made non-adhesive by a treatment such as powdering andpost-chlorination, followed by winding with human hands. This makes itimpossible to maintain the high cleanness of the product and it isdifficult to use the conventional fingerstall in a workplace whereprecisely processed articles are manufactured. The present invention,however, which is able to make the both surfaces of the latex moldingnon-adhesive, can afford to mechanically wind the fingerstall on thedipping former and can maintain the high cleanness of the product.

[0180] Recently, a thin fingerstall is desired since wearing a thick onetends to cause tiredness. The thinner the fingerstall the more difficultto wear it, so desired is a wound fingerstall that is thin, powder-free,non-adhesive and clean.

[0181] By utilizing the property that the both surfaces of thefingerstall are non-adhesive, fingerstalls with wound mouth can easilybe manufactured. In manufacturing the fingerstall, the top of the stallis left adhesive without providing the layer of the carboxyl groupblocking agent, the whole is wound up, and then unwound. The portionhaving adhesion remains as a wound mouth. Hitherto, the wound mouth hasbeen formed first by winding up only the top of the stall to make thewound mouth, and thereafter the stall has been released from the formerin another step. The wound mouth facilitates wear and removal of thestall and is highly desired for flat products. Further, after formationof the wound mouth according to the prior art, non-adhesion treatmentcan be conducted to achieve the objective.

[0182] Further, the wound mouth can be provided for the woundfingerstall mentioned in the previous paragraph.

Example

[0183] The present invention is explained in detail using exampleshereinafter, but the invention is not limited to the examples. Thepercentage and the part shown in the examples are a weight percentageand a weight part unless otherwise indicated. Further, in the examplesmentioned below, unless otherwise shown, the latex film was prepared bythe dipping method from the viewpoint of easiness of the experiments andeasiness of confirming the effect. The present invention, however, isnot limited to the dipping products.

[0184] Preparation of Latex Film

[0185] Using a test tube-like, glass-made dipping former for makingfingerstall, a latex film was prepared. When an external coagulant and acarboxyl-group blocking agent of solution types were used, asand-blasted glass-made dipping former was used. When a powderycarboxyl-blocking agent was used, a transparent glass-made dippingformer not subjected to sand blasting was used. First, the dippingformer was dipped in the external coagulation liquid to attach theliquid and dried. Next, the dipping former was dipped in a latexemulsion to form a latex film, and then drying, leaching andvulcanization treatment were conducted according to the conventionalmethod.

[0186] In the case of treating the outside surface of the film, thedipping former affixed with the film is again dipped in a solution orsuspension liquid of the carboxyl group blocking agent, followed bydrying and leaching treatment.

[0187] As the latex, a carboxylated NBR, NIPOL LX-551, made by NipponZeon was used unless specially mentioned. The latex is not limited tothis.

[0188] The properties of LX551 are shown below. Solids 45% PH 8.5Viscosity 85 mPs Gel content 0% Tg −14° C. Conbined AN content 37%

[0189] To 100 parts of the above-mentioned latex, fine zinc flower wasadded as a vulcanizing agent, and the mixture was subjected to the test.

[0190] Adhesion Test of Latex Film-1

[0191] The adhesion of the latex film is highest when the film is heatedin the water-containing state.

[0192] After the leaching step following the non-adhesion treatment ofthe outside surface in the film manufacturing process, the latex film iswound on the dipping former and removed from the dipping former as itstands. This sample is heated in a hot air dryer at 70° C. for 30minutes, taken out and unwound after cooling. The film is thick becauseit is wound, and the sample is always in the wet condition during thetest. Accordingly, if the both surfaces of the film are non-adhesive,unwinding is easy, and if adhesive, unwinding is difficult.

Comparative Example 1

[0193] Preparation of External Coagulation Solution

[0194] A solution of calcium nitrate tetrahydrate 150 g and water ormethanol 1000 g was prepared to make an external coagulant (hereinaftercalled coagulant 1).

[0195] Manufacture of Latex Film

[0196] A sand-blasted glass pipe is dipped in the aqueous externalcoagulant 1 and dried. The glass pipe attached with the externalcoagulant is dipped in a latex emulsion to form a latex film. The filmaffixed on the dipping former is dried softly at 50° C. for 3 minutesand further subjected to the leaching treatment for 3 minutes in the hotwater of 70° C. Subsequently, the film is wound on the former andreleased from the former. The film is unwound and subjected tovulcanization treatment in a hot air dryer at 120° C. for 30 minutes tomake samples for testing strength. For the adhesion test, the samplewound and removed from the former was presented as it stood. The testresults of film strength and adhesion are shown in Table 1.

[0197] The sample after the adhesion test could not be unwound.

Example 1

[0198] The film formed in Comparative Example 1 is leached, releasedfrom the former, unwound, dipped in an aqueous solution ofpolyaluminumchloride (which is an external crosslinking agent)containing 2.5% as alumina and immediately taken out. At this time thefilm surface already has lost adhesiveness and gives a feeling ofsmoothness. This film is dried at 70° C. for 3 minutes, furthersubjected to leaching treatment in the hot water at 70° C. for 3minutes, and subjected to vulcanization treatment in the same manner asComparative Example 1. The results of strength test of the film areshown in Table 1. For the adhesion test, the film, which underwentleaching treatment after non-adhesion treatment of the outside surface,was again placed on the former. The film was wound to make test samples.The sample after the adhesion test could easily be unwound.

Example 2

[0199] The dipping former was dipped in a solution of polyaluminumchloride (which is an external coagulant) containing 2.5% as alumina andused in Example 1 , attached, then dried, next dipped in the externalcoagulant methanol solution 1, attached and dried. The dipping formerwas dipped in the latex liquid to form a film, then dried at 50° C. for3 minutes and further subjected to leaching treatment at 50° C. for 3minutes. Thereafter the former was again dipped in the aqueous solutionof polyaluminum chloride used in Example 1 in order to prevent theadhesion of the film outside surface and subjected to leaching treatmentand vulcanization treatment. The test results on the film strength areshown in Table 1. The sample after the adhesion test was able to beunwound easily. This shows that the inside surface contacting thedipping former has become non-adhesive. The outside surface isnon-adhesive, as in Example 1.

Example 3

[0200] Except that aluminum acetate containing 2.4% as alumina was usedin place of polyalunimun chloride which is attached to the dippingformer and in which the formed film is dipped, the latex film wasprepared as with Example 2. Table 1 shows the test results on thestrength of the film. The film wound in the adhesion test could easilybe unwound.

Example 4

[0201] Using aluminum nitrate containing 0.2% alumina and a solutioncontaining calcium nitrate tetrahydrate 150 g and methanol 1000 g asexternal coagulation liquid and external crosslinking liquid, a film wasproduced. Then, there was conducted adhesion preventing treatment of theoutside surface of the film according to the same operation as inExample 2. The film thickness was approximately equal to that ofComparative Example 1 and Example 2. The test results on the strength ofthe film are shown in Table 1. In this case too, as with Example 2, thesample after the adhesion test could easily be unwound.

Comparative Example 2

[0202] The dipping former was dipped in the external crosslinking agent,polyaluminum chloride solution, used in Example 1, and a film was formedin the same manner as Comparative Example 1. The film thickness was only0.03 mm, and polyaluminum chloride was found to be unsuitable asexternal coagulant. Using various aluminum compounds such as aluminumchloride, aluminum nitrate and aluminum acetate, the same tests as abovewere conducted. The results were the same.

Comparative Example 3

[0203] The order of attaching the external crosslinking agent and theexternal coagulant in Example 2 was inverted, and dipping treatment wasconducted so that the layer of polyaluminum chloride might come outside.The thickness of the film was only 0.04 mm, being similar to ComparativeExample 2. This formulation was unsuitable for external coagulantformulation.

Reference Example 1

[0204] Except that fine zinc flower was not added in the emulsion latex,a latex film was prepared in the same way as Example 3. As with Example3, the film formed had a usual thickness, and the both surfaces of thefilm were non-adhesive. On the other hand, the strength of the film wasextremely low. This fact can be interpreted as that the aluminumcrosslinking layers are extremely thin and it does not contribute to thefilm strength.

Comparative Example 4

[0205] Except that an aqueous solution of zinc nitrate containing 5% aszinc oxide was used in place of polyaluminum chloride, a latex film wasprepared in the same way as Example 1. The film was adhesive, and it wasimpossible to carry out unwinding after the adhesion test. Zinc isbivalent and insufficient to make the film non-adhesive.

[0206] Table 1 shows the test results on the film strength.

Example 5

[0207] An aqueous solution of sodium aluminate and an aqueous solutionof calcium nitrate were mixed to prepare calcium aluminate. A solutionof water/methanol(1/1) was prepared to make calcium aluminate 20 g/1000g (calculated as anhydride) and calcium nitrate tetrahydrate 150g/1000g.

[0208] A transparent glass-made dipping former was dipped in saidexternal coagulation liquid, a coagulant layer was formed on the formerusing calcium aluminate as support, and thereafter a latex film wasprepared in the same way as Example 2.

[0209] On the dipping former calcium aluminate remains thinly, but whenthe inside surface after vulcanization is observed, the calciumaluminate is hardly recognized. The sample after the adhesion test couldbe unwound. The test results of the film strength are shown in Table 1.

[0210] When the dipping former is vigorously shaken immediately afterthe film is formed through dipping in the emulsion latex, the filmbreaks down. Under the layer broken down, a very thin aluminum treatmentlayer is recognized. Taking into consideration this fact and ReferenceExample 1, it is understandable that the aluminum treatment layer is avery thin layer.

Example 6

[0211] Dry aluminum hydroxide gel made by Tomita Seiyaku Co. wasdispersed with a ball mill for 24 hours and then added with water andmethanol so that a suspension of aluminum hydroxide 20 g (calculated asanhydride) in 1000 g water/methanol (1/1) and calcium nitratetetrahydrate 150 g in 1000 g water/methanol(1/1) is prepared. Thereaftera latex film was formed in the same way as Example 5. The test resultson strength are shown in Table 1. The wound film could easily be unwoundas with Example 4.

[0212] In the process of heating the film it is observed that aluminumhydroxide is absorbed in the latex film.

Comparative Example 5

[0213] There was prepared a suspension solution of water/methanol (1/1)having light calcium carbonate 100 g/1000 g, bentonite 50 g/1000 g andcalcium nitrate tetrahydrate 150 g/1000 g. A latex film was manufacturedin the same way as Example 5.

[0214] The wound latex film could not be unwound even before heating.The sample for testing the strength was prepared using talc as thepowder.

Comparative Example 6

[0215] Except that 1 part of aluminum hydroxide used in Example 6(calculated as anhydride) was added in 100 parts of a latex, a latexfilm was made in the same manner as Comparative Example 1. The woundfilm could not be unwound.

Example 7

[0216] Using an aqueous solution containing 0.2% aluminum nitrate (asalumina) and 150 g calcium nitrate tetrahydrate in 1000 g water asexternal coagulant and concurrently as external crosslinking agent, alatex film was fabricated. Thereafter, the outside surface of the filmwas dipped in an aqueous solution of zirconyl acetate, 1.5% as ZrO₂, andthe leaching and vulcanization treatment were conducted in the samemanner as Example 2. The results of strength test on the film are shownTable 1. The sample after the adhesion test could easily be unwound.

Example 8

[0217] Using an aqueous solution containing 0.2% zirconyl nitrate (asZrO₂) and 150 g calcium nitrate tetrahydrate in 1000 g water as externalcoagulant and concurrently as external crosslinking agent, a latex filmwas prepared. Thereafter, the outside surface of the film was dipped inan aqueous solution of polyaluminum choloride (2.5% as alumina),leaching and vulcanization treatments were conducted in the same manneras Example 2. The results of the strength test for the film are shown inTable 1. The sample after the adhesion test could easily be unwound.

Example 9

[0218] A latex film was prepared in the same manner as Example 7 exceptthat an aqueous solution of titanium lactate of 1.5% as TiO₂ was used inplace of zirconyl acetate. The results of strength test of the film areshown in Table 1. The sample after the adhesion test could easily beunwound.

Example 10

[0219] An adhesion test of the latex film was conducted in the same wayas Example 4 except that carboxylated SBR (SBR 2570X5 made by NipponZeon Co.) was used in place of NBR. The sample after the adhesion testcould easily be unwound. Zinc oxide was not incorporated in SBR in theexperiment.

Example 11

[0220] Except that carboxylated CR latex mentioned below was used inplace of NBR, a latex film was prepared in the same manner as in Example5. The results of the strength test for the films are shown in Table1.The sample after the adhesion test could easily be unwound. CarboxylatedCR latex made by Toso Co. GFL-280 60 parts LA-502 40 parts

[0221] The pH and viscosity of the formulation latex was 8.9 and 37.8mPs, respectively.

Comparative Example 7

[0222] A film was formed using the carboxylated CR latex used in Example10 and using calcium nitrate as external coagulant. The film thus formedhad strong adhesiveness and was impossible to remove from the dippingformer. The latex finds an application as an adhesive. TABLE 1 Thicknessof film Maximum load Maximum load (mm) stress (kgf/cm²) strain (%)Adhesion test Remarks Example 1 0.11 390 680 Possible to unwind Example2 0.12 370 695 Possible to unwind Example 3 0.12 370 680 Possible tounwind Example 4 0.12 380 690 Possible to unwind Example 5 0.13 480 790Possible to unwind Example 6 0.09 450 720 Possible to unwind Example 70.11 290 700 Possible to unwind Example 8 0.10 300 720 Possible tounwind Example 9 0.11 310 680 Possible to unwind Example 11 0.12 2561040 Possible to unwind Example 12 0.12 340 732 Possible to unwind Easyto wear Example 13 0.11 350 650 Possible to unwind Very easy to wearReference Example 1 0.09 30 640 Possible to unwind Poor strengthComparative Example 1 0.12 410 690 Impossible to unwind ComparativeExample 2 0.03 Not determined Not determined Not tested Defect of filmthickness Comparative Example 3 0.04 Not determined Not determined Nottested Defect of film thickness Comparative Example 5 0.08 530 750Impossible to unwind Comparative Example 6 0.07 490 760 Impossible tounwind

Example 12

[0223] There was fabricated a trial equipment for manufacturingfingerstalls shown in FIG. 2 which is equipped with a dipping formertransferring apparatus (see Japanese Patent Application Laying-Open(kokai) No.7-329084). Using this equipment, fingerstalls were producedin the same manner as Example 2 to Example 6. The dipping formertransferring apparatus of FIG. 1 transfers the dipping former 3 with itschain 1 being moved along the guide rail 2.

[0224] The rod 4 moves along the guide 5 and enables the dipping former3 to move upwards and downwards. In FIG. 2, when the dipping former 3passes through the dipping tank 6, the dipping former 3 is dipped in thedipping tank with its being lowered. Each of external crosslinkingsolution tank, external coagulation solution tank, latex liquid tank andleaching treatment tank is made ready previously, the tanks are switchedwhere deemed necessary, and each dipping treatment and leachingtreatment are carried out. After each dipping treatment and leachingtreatment, the dipping former 3 is transferred to the drying furnace 7and dried. Except when the winding machine 8 and the unwinding machine 9are used, the dipping former 3 is kept so that it does not comedownwards and kept so that it does not come into contact with thewinding machine 8 and the unwinding machine 9. At the time of drying andleaching treatment, the dipping former 3 is stopped to undergo treatmentfor a predetermined period. The winding machine 8 rotates a roll typebrush 10 (FIG. 3) previously set up obliquely, and by passing thedipping former through the brush the film 11 affixed on the dippingformer 3 is wound. After leaching and subsequent drying treatments, thedipping former 3 is passed through the winding machine 8, and the filmdeposited onto the dipping former is wound, being removed from theformer.

[0225] The wound fingerstall was dried at 70° C. for 120 minutes to makethe product. This stall was easy to wear on finger. Regarding to thetest for film strength, the wound film was immediately unwound, dried at70° C. for 60 minutes and subjected to the test.

Example 13

[0226] In the same way as in Example 12, the dipping former was passedthrough the winding machine, and the wound fingerstall was unwound bythe unwinding machine 9. The unwinding machine 9, as shown in FIG. 4,rotates a roll type brush 10, and when the dipping former 3 is passedthere, the machine unwinds the film 11 wound by the winding machine 8.The unwound fingerstall was dried in the drying furnace 7 at 90° C. for5 minutes. After drying, the stall was again treated on the windingmachine 8 and removed from the former to obtain the product.

[0227] This method of manufacturing the stall is evaluated to be highlypractical, because the drying of the product is easy and the stall iseasy to wear on finger because the winding operation is conducted twice.For the film strength test, the films were dried at 90° C. for 5 minutesprior to testing.

Example 14

[0228] In the same way as in Example 12 and 13 there were preparedfingerstalls wound by the winding machine 8, but the manufacturconditions were changed as follows. Namely, the dipping former wasdipped in the latex liquid 1 cm more deeply than the portion depositedwith the coagulant. Further, it was dipped in the external crosslinkingagent 2 mm more shallowly than the portion where the coagulant isdeposited. When these stalls are unwound, the non-adhesive portionsremain as a wound mouth. The unwound fingerstalls became straightfingerstalls with wound mouth and the fingerstalls before unwindingbecame wound fingerstalls with wound mouth.

Example 15

[0229] Wear Durability Test

[0230] The fingerstall of a non-adhesive carboxylated latex vulcanizedwith zinc oxide gave very good strength in the strength test. But it wasfound that, when it was worn actually, the fingerstall film of theportion which was in contact with finger joints and finger bottoms brokein some cases in several hours. It is considered that expansion andcontraction occur during wear because of the ionic crosslinking and thatthe crosslink points gradually break. This phenomenon is hard to occurin the case of sulfur vulcanization which gives covalent bond.

[0231] So, a little slender, ten fingerstalls (16.5 mm in diameter) wereworn actually on the middle finger and the medical finger to investigatethe number of stalls which break after 24 hours. The results are shownin Table 2. When the emulsion latex is directly added with zinc oxideand the internally added aluminum type inorganic crosslinking agent suchas aluminate and aluminum hydroxide gel (0.10 to 0.30 part as Al₂O₃) andwhen vulcanization is conducted, surprisingly the fingerstalls did notbreak. Presumably, when the crosslink points of zinc break, aluminum ionmakes a crosslink and repairs. The results are shown in Table 2 (also,refer to Table 12.)

[0232] The latex film forming conditions were the same as the paragraphmentioned below. As a carboxyl group blocking agent for surfacetreatment, polyaluminumhydroxide (Paho#2S, an aqueous solution of 0.025%as Al₂O₃) was used, and the vulcanization temperature was 90° C.

[0233] The compounds used in examples are as follows: Aluminumhydroxidegel Aluminum hydroxide gel [Tomita] (made by Tomita Seiyaku Co.) Sodiumaluminate Sodium aluminate #2019 (made by Asada Kagaku Co.) Polyaluminumhydroxide Paho#2S (made by Asada Kagaku Co.)

[0234] TABLE 2 Example No. 15 Content of added NaAlO₂ 0 0.10 0.15 0.200.25 0.30 (as Al₂O₃) (part) Number of broken stalls after 10 5 2 0 0 024 hour-wearing Content of added aluminum- 0 0.10 0.15 0.20 0.25 0.30hydroxide gel (as Al₂O₃) (part) Number of broken stalls after 2 0 24hour-wearing

[0235] Screening of Carboxyl Group Blocking Agent

[0236] The following screening was conducted for carboxyl-group blockingagents for surface treatment other than the external crosslinking agentsof metal compounds having three or more valences. These compoundsgenerally have low reactivity with carboxyl group at low temperatures.Because of this, these compounds tend to diffuse in the Z-axis directionof the latex film in the steps of dipping and leaching treatments. Toreduce the influence of the diffusion of the carboxyl-group blockingagent and to restrain the reduction of the strength, the latex wasdiluted to half the neat and the concentration of calcium nitrate, anexternal coagulant, was increased to 300 g/1000 g from 150 g/1000 g.Further, as mentioned below, regarding the reaction temperature ofthe-latex film before the strength is expressed, since a highertemperature is desirable for the strength, the temperature of theleaching step was changed to 75° C. Further, to study the effect of thetemperature in the vulcanization step, the vulcanization temperature wasset at two levels of 90 and 120° C. The latex film forming conditionsand the adhesion test conditions are as follows, unless otherwisementioned.

[0237] Latex Film Forming Conditions

[0238] Raw material latex: carboxylated NBR Nipol LX-551

[0239] Vulcanizing agent: active zinc flower 1.5 parts Sodium aluminateor aluminum hydroxide 0.25 part (as Al₂O₃)

[0240] Solids concentration: adjusted to 22.5% by diluting with water(dilution, 1:2)

[0241] Coagulant: calcium nitrate tetrahyrate; 300 g/1000 g Carboxylgroup blocking agent: 0.025% or 0.0025% The dipping former is dipped inthe coagulant solution. The amount deposited onto the former is adjustedto 0.03 g.

[0242] Dipping: The dipping former attached with the coagulant is dippedin the latex solution. The dipping former is pulled up after 5 seconds

[0243] Primary drying: 50° C., 2 minutes

[0244] Leaching: 75° C., 3 minutes

[0245] Drying: 90° C., 1 minute

[0246] Outside surface treatment with carboxyl group blocking agent: Thelatex film is dipped in the outside surface treatment solution of 0.025%or 0.0025% carboxyl group blocking agent. The amount attached of thesurface treatment solution was 0.03 g.

[0247] Vulcanization: The latex film was vulcanized at 90 or 120° C. for5 minutes. The thickness of the latex film after vulcanization was 0.07to 0.08 mm, and the weight was 0.3g.

[0248] Adhesion Test-2

[0249] The latex film prepared under the above-mentioned conditions isvulcanized, wound on the dipping former, and removed from the former asit is. The sample is heated in a hot air dryer of 90° C. for 30 minutes.Then, the sample is taken out from the dryer, cooled and unwound. Themark ◯ indicates that unwinding is easy, the mark Δ indicates thatunwinding becomes difficult on the way, the mark X indicates thatunwinding is considerably difficult and the mark ◯′ indicates thatunwinding is slightly problematic.

Example 16 to 18

[0250] To confirm the effect of addition of the aluminum type inorganiccrosslinking agent that is internally added in the emulsion latex(aluminum hydroxide gel in Example 16 to 18, sodium aluminate in Example35 and 61), regarding the aluminum type external crosslinking agent forsurface treatment (aluminum nitrate and polyaluminumhydroxide in Example16, oxazoline compound in Example 17, and carbodiimide compound inExample 18), there was studied the effect of the concentration of thecarboxyl group blocking agent. Here, the vulcanization temperature ofthe aluminum type external crosslinking agent (aluminum nitrate orpolyaluminum hydroxide) was 90° C., and that of oxazoline andcarbodiimide compounds was 120° C.

[0251] In the case of the aluminum type external crosslinking agent,even when the emulsion latex is not added with the internally addedaluminum type inorganic crosslinking agent, the latex product becomesnon-adhesive. When the internally added aluminum type inorganiccrosslinking agent is used, the concentration of the carboxyl groupblocking agent for surface treatment is lowered.

[0252] On the other hand, in the case where the carboxyl group blockingagent for surface treatment is a water-soluble oxazoline compound orwater-soluble carbodiimide compound, if the internally added aluminumtype inorganic crosslinking agent is not added, the effect of thecarboxyl-group blocking agent for surface treatment is small. However,although classified as compounds of the same kind, in the case ofemulsion type carboxyl group blocking agent for surface treatment, evenwhen the internally added aluminum type inorganic crosslinking agent isnot added, the non-adhesion effect is obtained. In the case ofwater-soluble carboxyl group blocking agent for surface treatment, thecarboxyl-group blocking agent diffuses in the Z-axis direction to resultin a small effect of the carboxyl-group blocking agent. On the otherhand, if the internally added aluminum type inorganic crosslinking agentis added, the diffusion of the carboxyl-group blocking agent isrestrained, and thus non-adhesion effect appears. The results are shownin Table 3. The compounds used in this example are as follows.

[0253] Aluminum hydroxide gel: aluminum hydroxide gel[Tomita] (made byTomita Seiyaku Co.)

[0254] Polyaluminum hydroxide: Paho#2S (made by Asada Kagaku Kogyo Co.)

[0255] Oxazoline compound: Epocross W (aqueous solution) (made by NihonShokubai Co.) Epocross K-2030(emulsion) (made by Nihon Shokubai Co.)

[0256] Carbodiimide compound: Carbodilite E-01 (emulsion) (made byNisshinbo Co.)

[0257] Carbodilite V-02(aqueous solution) (made by Nisshinbo Co.)

[0258] Example 35 used a modified polyamine polyurea resin (SumirezResin 712). This resin is so reactive that it causes the latex tocoagulate when added to the latex. In the case of such a compound, as inthe aluminum type external crosslinking agent, non-adhesion effectappears in even a system to which the internally added aluminum typeinorganic crosslinking agent is not added. Further, alkylketene dimer ofExample 61 is an emulsion and is reactive, and, as with the emulsion ofExample 17 and 18, even the system in which the internally addedaluminum type inorganic crosslinking agent is not added possesses thenon-adhesion effect. TABLE 3 Content of internally added aluminumCarboxyl-group type inorganic Example blocking agent for crosslinkingagent Vulcanization Concentration of chemical No. surface treatmentTrademark (as Al₂O₃)(part) temp. 1.0% 0.25% 0.025% 0.0025% 0.001% 16Aluminum Al(NO₃)₃ Aluminum 0 90° C. ∘ ∘ ∘′ x compound (aq. solution)hydroxide 0.25 90° C. ∘ ∘ Δ Paho#2S gel 0 90° C. ∘ ∘ x (polyaluminumhydroxide) 0.25 90° C. ∘ ∘ Δ (aq. solution) 17 Oxazoline Epocross K20300 120° C. ∘ Δ compound (emulsion) 0.25 120° C. ∘ ∘ ∘ Epocross W 0 120°C. x x (aq. solution) 0.25 120° C. ∘ ∘ ∘ ∘ 18 Carbodiimide CarbodiliteE-01 0 120° C. ∘ ∘ Δ compound (emulsion) 0.25 120° C. ∘ ∘′ Δ CarbodiliteV-02 0 120° C. Δ x (aq. solution) 0.25 120° C. ∘ ∘ Δ 35 Modified SumirezResin 712 Sodium 0 90° C. ∘ ∘ ∘ x Polyamine polyurea (aq. solution)aluminate 0 120° C. ∘ ∘ ∘ x resin 0.25 90° C. ∘ ∘ ∘′ 0.25 120° C. ∘ ∘ ∘′61 Alkylketene dimer Hasize AK-720H 0 90° C. ∘ ∘ ∘ (emulsion) 0 120° C.∘ ∘ ∘ 0.25 90° C. ∘ ∘ 0.25 120° C. ∘ ∘

Example 19

[0259] Next, to study the influence of the diffusion of the carboxylgroup blocking agent for surface treatment, there was studied the effectof a temperature of the leaching step before vulcanization.

[0260] As the carboxyl-group blocking agent, the water-soluble oxazolinecompound (Epocross W, made by Nippon shokubai Co.) was used. Theconcentration was varied from 0.1% to 0.001%, and the temperature of theleaching step was varied from 50 to 75° C. The results are shown inTable 4.

[0261] In the case of the treatment concentration as high as 0.1%, whenthe leaching step temperature is low, the strength becomes low and thenon-adhesion effect tends to be low.

[0262] It is considered that, even in the case that the internally addedaluminum type inorganic crosslinking agent (sodium aluminate, 0.25 partas Al₂O₃) was added, there appeared the influence of the diffusion inlow temperatures. TABLE 4 Carboxyl-group crosslinking organic Exampleagent for surface Temp. of leaching step No. treatment Conc. 50° C. 55°C. 60° C. 65° C. 70° C. 75° C. 19 Oxazoline compound 0.1% Adhesion testX ◯ ◯ ◯ ◯ Epocross W Strength (Mpa) 27.9 31.8 29.8 30.5 37.7 0.025%Adhesion test X ◯ ◯ ◯ ◯ ◯ Strength (Mpa) 37.3 0.005% Adhesion testStrength (Mpa) 35.1 0.001% Adhesion test X ◯ Strength (Mpa) 35.1

Examples 20 to 27

[0263] Regarding to the compounds considered as crosslinking agents forcarboxyl group, there was studied how the concentration of the carboxylgroup blocking agent for surface treatment and the vulcanizationtemperature (90 and 120° C.) had effect on the non-adhesion in thesystem in which the internally added aluminum type inorganiccrosslinking agent was added. The test results are shown in Table 5.

[0264] Carboxyl group blocking agents for surface treatment (i.e.,organic crosslinking agents for carboxyl group):

[0265] (Example 20) polyamine triethylenetetramine(made by Wako Seiyaku)

[0266] (Example 21) melamine resin, Sumitex Resin M-3 (made by SumitomoKagaku Kogyo)

[0267] (Example 22) melamine resin, Sumirez Resin 613 special (made bySumitomo Kagaku Kogyo)

[0268] (Example 23) amino group-containing urethane resin, SuperflexR-3000 (made by Daiichi Kagaku Kogyo)

[0269] (Example 24) blocked isocyanate prominate, XC-915 (made by TakedaYakuhin Kogyo)

[0270] (Example 25) multifunctional epoxy compound, Denacol EX-614B(made by Nagase Kasei Kogyo)

[0271] (Example 26) epoxycresolnovolac resin emulsion, Denacol EM-150(made by Nagase Kasei Kogyo)

[0272] (Example 27) bifunctional epoxy compound, Denacol EX-313 (made byNagase Kasei Kogyo) TABLE 5 Carboxyl-group crosslinking organic Exampleagent for surface Vulcanization Conc. of organic crosslinking agent No.treatment Trademark temp. 0.025% 0.01% 0.005% 0.0025% 20 PolyamineTriethyltetramine 90° C. ∘ 120° C. Δ 21 Melamine resin Sumitex Resin M-390° C. ∘ 120° C. Δ 22 Melamine resin Sumitex Resin 613special 90° C. ∘ ∘120° C. ∘ 23 Amino group-containing Superflex R-3000 (urethane) 90° C. ∘∘ urethane resin 120° C. ∘ 24 Blocked isocyanate Prominate XC-915 90° C.∘ 120° C. ∘ 25 Polyfunctional epoxy Denacol EX-614B 90° C. Δ ∘ ∘′compound 120° C. ∘ ∘ 26 Epoxycresolnovolac resin Denacol EM-150 90° C. ∘∘ 120° C. ∘ ∘ 27 Bifunctional epoxy Denacol EX-313 90° C. ∘ ∘ compound120° C. ∘

Examples 28 to 36

[0273] In the same manner as in Example 20 to 27, regarding the hydrogenbond formation regulators used in the field of paper, the test wasconducted to evaluate their performance as carboxyl group blockingagent. These compounds have been developed as waterproof endowing agent,printability improver, wet paper strength reinforcing agent and the likeof papers, with their workability and safety taken into consideration.The results are shown in Table 6. As in the case of the organiccrosslinking agent for carboxyl group, the compounds give thenon-adhesion effect.

[0274] As to Example 35, the test was conducted for the system in whichthe internally added aluminum type inorganic crosslinking agent, sodiumaluminate, was not added.

[0275] Carboxyl group blocking agent for surface treatment (i.e.,hydrogen bond formation regulators):

[0276] (Example 28) glyoxal (made by Wako Junyaku Co.)

[0277] (Example 29) polyamide resin, Sumirez Resin 5001 (made bySumitomo Kagaku Kogyo Co.)

[0278] (Example 30) polyamide resin, Sunmide X-13A (made by Sanwa KagakuKogyo Co.)

[0279] (Example 31) polyamidepolyurea resin, Sumirez Resin 636 (made bySumitomo Kagaku Kogyo Co.)

[0280] (Example 32) polyamideepoxy resin, Sumirez Resin 675 (made bySumitomo Kagaku Kogyo Co.)

[0281] (Example 33) polyaminepolyurea resin, Sumirez Resin 302 (made bySumitomo Kagaku Kogyo Co.)

[0282] (Example 34) polyaminepolyurea resin, PA-620 (made by Nippon PMC)

[0283] (Example 35) modified polyaminepolyurea resin, Sumirez Resin 712(made by Sumitomo Kagaku Kogyo Co.)

[0284] (Example 36) polyamidepolyureaglyoxal condensation reactionproduct, Sumirez Resin 5004 (made by Sumitomo Kagaku Kogyo Co.) TABLE 6Example Hydrogen bond formation Vulcanization Conc. of reactive organiccompound No. regulator for surface treatment Trademark temp. 0.025%0.01% 0.005% 0.0025% 28 Glyoxal 90° C. Δ 120° C. ∘ 29 Polyamide resinSumirez Resin 5001 90° C. ∘ ∘ ∘ 120° C. ∘ ∘ 30 Polyamide resin SunmideX-13A 90° C. ∘ 120° C. ∘ 31 Polyamide polyurea resin Sumirez Resin 63690° C. ∘ ∘ 120° C. ∘ ∘ 32 Polyamide epoxy resin Sumirez Resin 675 90° C.∘′ 120° C. ∘ 33 Polyamine polyurea resin Sumirez Resin 302 90° C. ∘ ∘′120° C. ∘ ∘ 34 Polyamine polyurea resin PA-620 90° C. ∘ 120° C. ∘ 35Modified polyamine polyurea Sumirez Resin 712 90° C. ∘ ∘ ∘′ resin 120°C. ∘ ∘′ NaAlO₂ 90° C. ∘ x not added 120° C. ∘ x 36Polyamidepolyureaglyoxal Sumirez Resin 5004 90° C. ∘ ∘′ ∘ condensationreaction product 120° C. ∘

Examples 37 to 39

[0285] The test was conducted in the same manner as in Example 20 to 34concerning the monofunctional carboxyl group blocking agent. The resultsare shown in Table 7. The agent, which is monofunctional, cannotcrosslink a carboxyl group, and yet it has the non-adhesion effect. Itis noticed that blocking a carboxyl group and forming hydrophobicity areboth important for the non-adhesion of the latex product.

[0286] Surface carboxyl blocking agents for surface treatment (i.e.,monofunctional carboxyl blocking agents):

[0287] (Example 37) monofunctional modified bisphenol A type epoxyemulsion, Denacast EM-103 (made by Nagase Kasei Kogyo Co.)

[0288] (Example 38) monofunctional modified bisphenol A type epoxyemulsion, Denacast EM-103 (made by Nagse Kase Kogyo Co.)

[0289] (Example 39) monofunctional epoxy, Denacol EX-145 (made by NagaseKasei Kogyo Co.) TABLE 7 Monofunctional carboxyl-group blocking Conc. ofmonofunctional Example agent for surface Vulcanization carboxyl-groupblocking agent No. treatment Trademark temp. 0.025% 0.01% 0.005% 0.0025%37 Monofunctional epoxy Denacast EM-101 90° C. ∘ (emulsion) 120° C. ∘ 38Monofunctional epoxy Denacast EM-103 90° C. ∘ ∘ ∘′ (emulsion) 120° C. ∘∘ 39 Monofunctional epoxy Denacol EX-145 90° C. ∘ 120° C. ∘

Examples 40 to 58

[0290] In the same manner as in Example 20 to 39, the non-adhesionsurfactants (cationic, amphoteric, nonionic, or anionic) were tested fortheir performance as carboxyl-group blocking agents, including a testfor the effect of adding an internally added aluminum type inorganiccrosslinking agent, sodium aluminate. The results are shown in Table 8 .In the system in which sodium aluminate was not added, the non-adhesioneffect of the surfactant is small.

[0291] Carboxyl group blocking agent for surface treatment (non-adhesivesurfactant):

[0292] Non-adhesion cationic surfactant:

[0293] (Example 40) quarternary amine, Quartermin 86W (made by Kao Co.)

[0294] (Example 41) quarternary amine, Catinal MB 50A (made by TohoKagaku Kogyo)

[0295] (Example 42) imidazoline type betaine, Anhitol 20YB (made by Kao)

[0296] (Example 43) oxide type betaine, Softamin L (made by Toho KagakuKogyo)

[0297] (Example 44) alkylamide type betaine, Ovazolin CAB-30 (made byToho Kagaku Kogyo)

[0298] Non-adhesive nonionic surfactant:

[0299] (Example 45) tertiary amine, Esomin C/12 (made by Lion)

[0300] (Example 46) tertiary alkylamine, Amito 105 (made by Kao)

[0301] (Example 47) alkanolamide, Aminon PK-02S (made by Kao)

[0302] (Example 48) polyoxyethylenelauryether, Emulgen 109P (made byKao)

[0303] (Example 49) polyoxyethylene derivative, Emulgen A60 (made byKao)

[0304] Non-adhesive anionic surfactant:

[0305] (Example 50) β-naphthalenesulfonic acid formalin condensationproduct, Demol N (made by Kao)

[0306] (Example 51) alkylmethyltaurinate, Lipotac TE (made by Lion)

[0307] (Example 52) disodium dodecyldiphenylethersulfonic acid, PerexSS-L (made by Kao) TABLE 8 Example Non-adhesive surfactant forVulcaniza- Conc. of surfactant No. surface treatment Trademard tion0.025% 0.01% 0.005% 0.0025% 40 Cation Quarternary amine Quatermin 86W90° C. ∘ 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. x 41 CationQuarternary amine Catinal MB-50A 90° C. ∘′ ∘′ 120° C. ∘ ∘ NaAlO₂ 90° C.x x not added 120° C. x x 42 Amphoteric Imidazoline type betaine Anhitol20YB 90° C. ∘ ∘′ Δ 120° C. ∘ NaAlO₂ 90° C. x x x x not added 120° C. x Δ43 Amphoteric Oxide type betaine Softamin L 90° C. Δ ∘ 120° C. ∘ ∘NaAlO₂ 90° C. x x not added 120° C. x x 44 Amphoteric Alkylamide typebetaine Ovazolin CAB-30 90° C. ∘ ∘ 120° C. ∘ NaAlO₂ 90° C. x x not added120° C. x 45 Nonion Tertiary alkylamine Esomin C/12 90° C. ∘′ ∘′ 120° C.∘ ∘ NaAlO₂ 90° C. x x not added 120° C. x x 46 Nonion Tertiaryalkylamine Amito 105 90° C. Δ 120° C. ∘ NaAlO₂ 90° C. x not added 120°C. x 47 Nonion Alkanolamide Aminon PK-02S 90° C. ∘ ∘ Δ(lauryldiethanolamide) 120° C. ∘ NaAlO₂ 90° C. x x x not added 120° C. x48 Nonion Polyoxyethylene laurylether Emulgen 109P 90° C. Δ 120° C. ∘NaAlO₂ 90° C. x not added 120° C. x 49 Nonion Polyoxyethylene derivativeEmulgen A60 90° C. Δ 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. x 50Anion β-naphthalenesulfonic acid Demol N 90° C. ∘ ∘′ formalincondensation 120° C. ∘ ∘ product NaAlO₂ 90° C. x x not added 120° C. x x51 Anion Alkylmethyltaurinate Lipotac TE 90° C. ∘′ Δ 120° C. ∘ NaAlO₂90° C. x x not added 120° C. x x 52 Anion Disodium Perex SS-L 90° C. Δdodecyldiphenylethersulfonate 120° C. ∘′ NaAlO₂ 90° C. x not added 120°C. x

Examples 53 to 58

[0308] Regarding the polymer type derivatives, to evaluate theirperformance as carboxyl group blocking agent, the test was conducted inthe same manner as in Example 40 to 52. Although these compounds aresometimes treated as polymer surfactant, they are employed asnon-adhesive polymer type surfactants in the present invention. Theresults are shown in Table 9.

[0309] Carboxyl group blocking agent for surface treatment (i.e.,non-adhesive polymer type surfactants):

[0310] (Example 53) cellulose derivative, Reoguard KGP (made by Lion)

[0311] (Example 54) cationized starch, CATO 308 (made by Nippon NSC)

[0312] (Example 55) cationized starch, Opti Bond 3282 (made by NipponNSC)

[0313] (Example 56) dimethyldiallyammoniumchloride acrylamide copolymer,ME polymer 09W (made by Toho Kagaku Kogyo)

[0314] (Example 57) cationic polyurethane dispersion in water, F-8570D(made by Daiichi Kogyo Seiyaku)

[0315] (Example 58) ammonium polystyrenesulfonate, VERSA-TLYE915 (madeby Nippon NSC) TABLE 9 Example Non-adhesive polymer surfactantVulcanization Conc. of polymer surfactant No. for surface treatmentTrademark temp. 0.025% 0.01% 0.005% 0.0025% 53 Cation Cellulosederivative Reoguard KGP 90° C. Δ 120° C. ∘ NaAlO₂ 90° C. x not added120° C. x 54 Cation Cationized starch CATO 308 90° C. ∘ Δ 120° C. ∘ ∘′NaAlO₂ 90° C. x not added 120° C. x 55 Cation Cationized starch OptiBond 3282 90° C. ∘′ 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. x 56Cation Dimethyldiallylammonium ME polymer 09W 90° C. ∘′ chlorideacrylamide 120° C. ∘ copolymer NaAlO₂ 90° C. x not added 120° C. x 57Cation Cationic polyurethane F-8570D 90° C. ∘ dispersion in water 120°C. NaAlO₂ 90° C. x not added 120° C. 58 Anion Ammonium VERSA-TLYE915 90°C. Δ polystrenesulforate 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. x

Examples 59 to 64

[0316] Regarding paper sizing agents, to evaluate their performance ascarboxyl group blocking agent, the test was conducted in the same way asin Example 20 to 39. The results are shown in Table 10. ConcerningExample 61, the test was conducted for the system in which theinternally added aluminum type inorganic crosslinking agent, sodiumaluminate, was not added.

[0317] Carboxyl group blocking agent for surface treatment (i.e., sizingagent):

[0318] (Example 59) fortified rosin, Sizepine E-50 (made by ArakawaKagaku Kogyo)

[0319] This sizing agent coagulates with a calcium salt. So, thetreatment of the inside surface was conducted with Sizepine N-773(concentration: 0.0025%) mentioned below, and the treatment of theoutside surface was conducted with Sizepine E.

[0320] (Example 60) emulsion type rosin sizing agent, Sizepine N-773(made by Arakawa Kagaku Kogyo)

[0321] (Example 61) alkylketene dimer, Hasize AK-720H (made by HarimaKasei)

[0322] (Example 62) styrene type synthetic sizing agent, BLS-720 (madeby Misawa Ceramics)

[0323] (Example 63) olefin type synthetic sizing agent, Hamacoat AK-505(made by Misawa Ceramics)

[0324] (Example 64) alkenyl succinate, Sizepine (made by Arakawa KagakuKogyo) TABLE 10 Example Sizing agent for surface Vulcanization Conc. ofsizing agent No. treatment Trademark temp. 0.025% 0.0025% 59 Fortifiedrosin sizing agent Sizepine E-50 90° C. ∘ 120° C. ∘ 60 Emulsion typerosin sizing Sizepine N-773 90° C. ∘ ∘ agent 120° C. ∘ ∘ 61 Alkylketenedimer Hasize AK-720H 90° C. ∘ ∘ 120° C. ∘ ∘ NaAlO₂ 90° C. ∘ not added120° C. ∘ 62 Styrene type synthetic BLS-720 90° C. ∘ ∘ sizing agent 120°C. ∘ ∘ 63 Olefin type synthetic sizing Hamacoat AK-505 90° C. ∘ ∘′ agent120° C. ∘ ∘ 64 Alkenyl succinate Sizepine S-400S 90° C. ∘ ∘ 120° C. ∘ ∘

Examples 65 to 81

[0325] The performance test was conducted for carboxyl group blockingagents in the same manner as in Example 20 to 64. The carboxyl-groupblocking agents were directly added to confirm their effect.Accordingly, the latex film was immediately vulcanized after theleaching treatment to make each sample. The adhesion test was conductedaccording to the adhesion test 2. The results are shown in Table 11. Itis noticed that any type of carboxyl group blocking agents for surfacetreatment is effective as an internally added carboxyl-group blockingagent. However, such a carboxyl-group blocking agent that coagulates thelatex when it is incorporated into a latex emulsion is not desirable. Insuch a case it is necessary to take a measure such as stabilizing thelatex emulsion by adding a surfactant. Also studied was the influence ofaddition of an internally added aluminum type inorganic crosslinkingagent, sodium aluminate. In the case of a reactive carboxyl-groupblocking agent (in Example 70 and 77) and a carboxyl-group blockingagent which forms an insoluble salt with calcium ion (in Example 76, 78and 81), the non-adhesion effect appears even in the system in whichsodium aluminate is not added. When a polyamide polyurea resin (SumirezResin 703) is added, the latex emulsion is coagulated without additionof sodium aluminate, but with addition of it, the sodium aluminatedisperses Sumirez Resin 703 homogeneously. Thus, without coagulation ofthe emulsified latex, the non-adhesion effect is observed.

[0326] Internally added carboxyl group blocking agents:

[0327] (Example 65) monofunctional modified bisphenol A type epoxyemulsion, Denacast EM-103 (made by Nagase Kasei Kogyo)

[0328] (Example 66) carbodiimide crosslinking agent, Carbodilite V-20(made by Toyobo)

[0329] (Example 67) oxazoline crosslinking agent, Epocross W (made byNihon Shokubai)

[0330] (Example 68) self-emulsifying type polyisocyanate, Aquanate 200(made by Nihon Polyurethane Kogyo)

[0331] (Example 69) blocked isocyanate, Prominate XC-915 (made by TakedaSeiyaku)

[0332] (Example 70) polyamide resin, Sumirez Resin 5001 (made bySumitomo Kagaku Kogyo)

[0333] (Example 71) polyamidepolyurea resin, Sumirez Resin 703 (made bySumitomo Kagaku Kogyo)

[0334] (Example 72) β-naphthalenesulfonic acid formalin condensationproducct, Demol N (made by Kao)

[0335] (Example 73) alkylnaphthalenesulfonic acid formalin condensationpolymerization product, Polyty N-100 (made by Lion)

[0336] (Example 74) alkylmethyltaurinate, Lipotac TE made by Lion)

[0337] (Example 75) emulsion type modified rosin sizing agent, HalfsizeNES-650 (made by Harima Kasei)

[0338] (Example 76) fortified rosin sizing agent, Sizepine (made byArakawa Kagaku Kogyo)

[0339] (Example 77) alkylketene dimer, Halfsize AK-720H (made by HarimaKasei)

[0340] (Example 78) alkenylsuccinate, Sizepine S-400S (made by ArakawaKagaku Kogyo)

[0341] (Example 79) alkenylsuccinic acid anhydride, Colopearl Z-100S(made by Seiko Kagaku Kogyo)

[0342] (Example 80) styrene acryl type surface sizing agent, ColopearlM-150-2 (made by Seiko Kagaku Kogyo)

[0343] (Example 81) saponification product of an adduct of branchedolefin and maleic anhydride, RFsize NSP-SH (made by Seiko Kagaku Kogyo)TABLE 11 Internally Example added carboxyl- Vulcanization Amount added(part) No. group blocking agent Trademark temp. 2.5 1.0 65Monofunctional epoxy Denacast EM-103 90° C. ∘′ x 120° C. ∘′ ∘ NaAlO₂ 90°C. x not added 120° C. x 66 Carbodiimide Carbodilite V-02 90° C. ∘′ ∘′120° C. ∘′ ∘ NaAlO₂ 90° C. x not added 120° C. x 67 Oxazoline Epocross W90° C. ∘ ∘′ 120° C. ∘ ∘ NaAlO₂ 90° C. x not added 120° C. x 68Self-emulsifying Aquanate 200 90° C. ∘′ polyisocyanate 120° C. ∘ NaAlO₂90° C. x not added 120° C. x 69 Blocked isocyanate Prominate XC-915 90°C. ∘ 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. Δ 70 Polyamide resinSumirez Resin 5001 90° C. ∘ ∘ 120° C. ∘ ∘ NaAlO₂ 90° C. Δ not added 120°C. ∘′ 71 Polyamide polyurea resin Sumirez Resin 703 90° C. ∘ ∘′ 120° C.∘ ∘ NaAlO₂ 90° C. aggregate not added 120° C. 72 β-naphthalenesulfonicDemol N 90° C. ∘ ∘′ acid formalin condensate 120° C. ∘ ∘ NaAlO₂ 90° C. xnot added 120° C. Δ 73 Alkylnaphthalenesulfonic Polyty N-100K 90° C. Δacid formalin condensate 120° C. ∘ NaAlO₂ 90° C. x not added 120° C. x74 Alkylmethyltaurinate Lipotac TE 90° C. ∘ x 120° C. ∘ ∘ NaAlO₂ 90° C.x not added 120° C. Δ 75 Emulsion type rosin Hasize NES-650 90° C. ∘′ Δsizing agent 120° C. ∘ ∘ (modified rosin) NaAlO₂ 90° C. x not added 120°C. Δ 76 Fortified rosin Sizepine E-50 90° C. ∘ x sizing agent 120° C. ∘∘ NaAlO₂ 90° C. Δ not added 120° C. ∘′ 77 Alkylketene dimer HasizeAK-720H 90° C. ∘ ∘ 120° C. ∘ ∘ NaAlO₂ 90° C. x not added 120° C. ∘′ 78Alkenyl succinate Sizepine S-400S 90° C. ∘ ∘′ 120° C. ∘ ∘ NaAlO₂ 90° C.∘′ not added 120° C. ∘ 79 Alkenyl succinic Coropearl Z-100S 90° C. ∘ ∘′acid anhydride 120° C. ∘ ∘ NaAlO₂ 90° C. x not added 120° C. Δ 80Styrene-acryl type Coropearl M-150-2 90° C. ∘ Δ surface sizing agent120° C. ∘ ∘ NaAlO₂ 90° C. x not added 120° C. Δ 81 Branchedolefin-maleic RF size NSP-SH 90° C. Δ anhydride adduct 120° C. ∘ NaAlO₂90° C. ∘′ not added 120° C. ∘

Examples 82 to 85

[0344] Fingerstalls were prepared in the same way as in Example 29except that internally added aluminum type inorganic crosslinking agentsas described below were used in place of sodium aluminate, and theadhesion and wear durability tests were conducted. The amount of theinternally added aluminum type inorganic crosslinking agent was 0.25part as Al₂O₃. The carboxyl-group blocking agent used was polyamideresin (Sumirez Resin 5001) . The concentration of the polyamide resinfor surface treatment was 0.025%. The results are shown in Table 12. Asin the case of Example 29, the latex film was non-adhesive. Anyfingerstall did not break in the wear durability test, thus passed thetest.

[0345] (Example 82) calcium aluminate (made by Soekawa Rikagaku)

[0346] (Example 83) magnesium aluminate (made by Soekawa Rikagaku)

[0347] (Example 84) aluminum magnesium hydroxide, Aluminum magnesiumhydroxide 251 (made by Tomita Seiyaku)

[0348] (Example 85) synthetic hydrotalcite, Synthetic hydrotalcite H(made by Tomita Seiyaku) TABLE 12 Internally added aluminum Example typeinorganic crosslinking Vulcanization Adhesion Number of No. agentTrademark temp. test 2 breakings 82 Calcium aluminate 90° C. Δ 0 120° C.∘ 0 83 Magnesium aluninate 90° C. Δ 0 120° C. ∘ 0 84 Aluminum ·magnesium Aluminum · 90° C. ∘ 0 hydroxide magnesium hydroxide 120° C. ∘0 251 85 Synthetic hydrotalcite Synthetic hydrotalcite 90° C. ∘′ 0 120°C. ∘ 0

Example 86

[0349] In manufacturing fingerstalls in the same way as in Example 2 and3, the dipping former was dipped and deposited with the externalcrosslinking agent for the inside surface, dried, and dipped in themethanolic external coagulant liquid 1 cm more deeply than the portionof said crosslinking agent and dried. Then the former was dipped in thelatex slightly more shallowly than the part of the methanolic externalcoagulation liquid, and further it was dipped in the externalcrosslinking liquid for the outside surface in the same depth as theexternal crosslinking agent for the inside surface. When these stallsare wound and then unwound, the non-adhesive portions remain as woundmouth. In this case, since the latex is not directly brought intocontact with the dipping former and since the thickness of the latex isincreased due to the coagulation liquid, the removal of the latex filmfrom the dipping former is easy and the winding is also easy.

Example 87

[0350] In forming fingerstalls in the same way as in Example 14 and 86,the wound mouth was formed after the former was dipped in the latex. Bycoating an external crosslinking liquid for the outer surface,non-adhesive fingerstalls with wound mouth could be formed. In thiscase, even if the former is immersed in the external crosslinking liquidmore deeply than the wound mouth portion, the wound mouth does notunwind and so it is not necessary to mind the depth of the externalcrosslinking liquid on the outer surface.

Example 88

[0351] In forming fingerstalls in the same way as in Example 4, theformer was immersed in the latex more shallowly than the externalcoagulation liquid and the external crosslinking liquid to form a woundmouth. As in Example 86, since the latex has an increased thicknessowing to the coagulation liquid, the removal of the latex-formed filmfrom the dipping former is easy and making the bottom windings is alsoeasy. In this case, if the latex is too dry when a wound mouth isformed, the wound mouth unwinds. But, if the wound mouth is made whenthe latex is half gelled, and if it is dried it does not unwind.

Example 89

[0352] Fingerstalls were formed using the trial-use fingerstallmanufacturing equipment (FIG. 2) under the same latex film formingconditions as in the said screening of carboxyl-group blocking agents.The former was immersed in the coagulation liquid and dried, andthereafter immersed in the latex incorporated with 1.5 parts of zincoxide, 0.25 part (as Al₂O₃) of sodium aluminate and 1.5 parts of zincoxide, and then dried. After subjected to the treatments ofmouth-winding, leaching and drying, the former was immersed in theoutside surface treating agent of 0.025% polyamide resin, Sumirez resin5001 (made by Sumitomo Kagaku Kogyo) and dried at 90° C. for 2 minutes.Thereafter, winding and unwinding were successively conducted, and, thefilm was dried at 90° C. for 3 minutes, again wound on the windingmachine and removed from the former in the wound state. In the case ofthe inorganic outside-surface treating agent, the leaching treatment isnecessary after immersion into the outside-surface treating agent. Sincethis outside-surface treating agent is organic, the leaching treatmentis unnecessary after the immersion into the outside-surface treatingagent. Hence, the manufacture steps can be reduced.

[0353] The stalls removed from the former were dried at 70° C. for 120minutes to give the final products. The formed stalls were easy to wearon finger.

Example 90

[0354] Fingerstalls were formed in the same way as in Example 86 exceptthat the latex was incorporated with 1 part of alkylketene dimer,Halfsize AK-720H (made by Harima Kasei) as carboxyl-group blockingagent. In this case, since the carboxyl-group blocking agent is added tothe latex, it is not necessary to deposite the outside-surface treatingagent after dipping the former into the latex. Hence, the manufacturesteps can be reduced. The manufacture steps are as follows. The formerwas dipped in the coagulation liquid and dried, then dipped in the latexand dried, subjected to a leaching treatment after winding the mouth,and dried at 90° C. at 2 minutes. Thereafter, winding and unwinding weresuccessively conducted, and the film was dried at 90° C. for 3 minutes.It was again wound on the winding machine and removed from the former inthe wound state.

[0355] The fingerstalls removed from the former was dried at 70° C. for120 minutes to give the final producta. The stalls were easy to wear onfinger.

[0356] Next, shown are examples of non-adhesive carboxylated latexproducts which have a layer treated with a carboxyl group blocking agenton the inside surface of the carboxylated latex products and which havea chlorination treatment on the outside surface thereof.

[0357] 1. Preparation of raw material latex

[0358] A raw material latex (carboxylated NBR Nipol LX-551, made byNippon Zeon) was added with 1.5 parts of activated zinc flower and 0.25part (as Al₂O₃) of aluminum hydroxide gel as vulcanizing agent. Themixture was diluted with water or water and a carboxyl group blockingagent to adjust the solids concentration to 22.5%.

[0359] 2. Preparation of coagulant solution

[0360] A coagulant aqueous solution of calcium nitrate tetrahydrate 300g/1000 g was prepared. When the inside surface was treated with acarboxyl group blocking agent, the carboxyl group blocking agent wasadded into the coagulant aqueous solution.

[0361] 3. Formation of film of carboxylated synthetic rubber latex

[0362] A former, which had been dipped in the coagulant liquid andattached with the coagulant, was dipped into a liquid of theabove-mentioned carboxylated synthetic rubber latex. After 5 seconds'residence, a latex film was formed. The thickness of the latex film was0.08 mm. The film was predried at 50° C. for 2 minutes and subjected toleaching treatment at 75° C. for 3 minutes. Then, the film was dried at90° C. for 1 minute, dipped into a chlorine aqueous solution having achlorine concentration of 0.4 g for 5 seconds, and thereafter heated at90° C. for 5 minutes. The latex film thus prepared was wound on theformer and removed from the former. This sample was subjected toadhesion test. The adhesion test was conducted by heating the sample, awound film, at 90° C. for 30 minutes and by unwinding after cooling. Thecase where the unwinding was easy was denoted by ◯, the case where theunwinding became not easy on the way by Δ,the case where the unwindingwas considerably difficult by X.

Comparative Example 8

[0363] With the above-mentioned conditions but without addition of thecarboxyl group blocking agent either in the coagulant or in the latex, alatex film was prepared only with chlorination treatment on the outsidesurface and subjected to the adhesion test. The results are shown inTable 13. The sample after the adhesion test was considerably difficultto unwind. TABLE 13 Internally added carboxyl-group blocking agent andCarboxyl- group blocking agent for surface Adhesion Comparative ExampleNo. treatment test 8 none x

Example 91

[0364] The results of the adhesion test of a sample, obtained byinternally adding in the latex a sizing agent as carboxyl group blockingagent and chlorinating the outside surface, are shown in Table 14. Thecarboxyl group blocking agent used in the example is as follows.

[0365] (Example 91) Fortified rosin sizing agent Sizepine E-50 (made byArakawa Kagaku Kogyo) TABLE 14 Internally added Amount Examplecarboxyl-group added Adhesion No blocking agent Trademark (part) test 91Fortified rosin Sizepine E-50 2.5 ∘ sizing

Examples 92-94

[0366] The results of the adhesion test of samples, obtained byinternally adding in the latex organic crosslinking agents as carboxylgroup blocking agent and chlorinating the outside surfaces, are shown inTable 15. The carboxyl group blocking agents used in the examples areeach as in the followings. TABLE 15 Internally added Amount Examplecarboxyl-group added Adhesion No blocking agent Trademark (part) test 92Blocked isocyanate Prominate 1 ∘ XC-915 93 Oxazorine Epocross 2.5 ∘WS-500 94 Monofunctional Denacast 2.5 ∘ epoxy EM-103

[0367] (Example 92) Blocked isocyanate Prominate XC-915 (made by TakedaYakuhin Kogyo)

[0368] (Example 93) Oxazoline crosslinking agent Epocross WS-500 (madeby Nippon Shokubai)

[0369] (Example 94) Monofunctional modified bisphenol A type epoxyemulsion Denacast EM-103 (Nagase Kasei Kogyo)

Example 95

[0370] The results of the adhesion test of a sample, obtained byinternally adding in the latex a surfactant as carboxyl group blockingagent and chlorinating the outside surface, are shown in Table 16. Thecarboxyl group blocking agent used in the example is as follows. TABLE16 Internally added Amount Example carboxyl-group added Adhesion Noblocking agent Trademark (part) test 95 β-naphthalenesurufonic demol N2.5 ∘ acid-formaline condensation product

[0371] Example 95) β-naphthalenesulfonic acid -formaline condensationproduct Demol N (made by Kao)

Example 96

[0372] The results of the adhesion test of a sample, obtained byinternally adding in the latex a hydrogen bond forming regulator ascarboxyl group blocking agent and chlorinating the outside surface, areshown in Table 17. The carboxyl group blocking agent used in the exampleis as follows.

[0373] (Example 96) Polyamidepolyurea resin Sumirez Resin 703 (made bySumitomo Kagaku) TABLE 17 Internally added Amount Example carboxyl-groupadded Adhesion No blocking agent Trademark (part) test 96 Polyamidepolyurea resin Sumirez 2.5 ∘ resin 703

Example 97

[0374] The results of the adhesion test of a sample, obtained by using asizing agent as carboxyl group blocking agent for treating the insidesurface and by chlorinating the outside surface, are shown in Table 18.The carboxyl group blocking agent used in the example is as follows.

[0375] (Example 97) Alkylketene dimer Hasize AK-720H (made by HarimaKasei) TABLE 18 Carboxyl-group blocking Concen- Example agent forsurface tration Adhesion No treatment Trademark (%) test 97 Alkylketendimer Hasize 0.025 ∘ AK-720H

Example 98

[0376] The results of the adhesion test of a sample, obtained by usingan organic crosslinking agent as carboxyl group blocking agent fortreating the inside surface and by chlorinating the outside surface, areshown in Table 19. The carboxyl group blocking agent used in the exampleis as follows.

[0377] (Example 98) Blocked isocyanate Prominate XC-915 (made by TakedaYakuhin Kogyo) TABLE 19 Carboxyl-group blocking Concen- Example agentfor surface tration Adhesion No treatment Trademark (%) test 98 Blockedisocyanate Prominate 0.025 ∘ XC-915

Example 99

[0378] The results of the adhesion test of a sample, obtained by using ahydrogen bond forming regulator as carboxyl group blocking agent fortreating the inside surface and by chlorinating the outside surface, areshown in Table 20. The carboxyl group blocking agent used in the exampleis as follows.

[0379] (Example 99) Polyamide resin Sumirez Resin 5001 (made by SumitomoKagaku) TABLE 20 Carboxyl-group blocking agent for surface ConcentrationAdhesion Example No treatment Trademark (%) test 99 Polyamide Sumirez0.025 ◯ resin resin 5001

Example 100

[0380] The results of the adhesion test of a sample, obtained by usingan aluminum compound as carboxyl group blocking agent for treating theinside surface and by chlorinating the outside surface, are shown inTable 21. The carboxyl group blocking agent used in the example is asfollows.

[0381] (Example 100) Polyaluminumhydroxide Paho#2S (made by Asada KagakuKogyo) TABLE 21 Carboxyl-group blocking agent for surface ConcentrationAdhesion Example No treatment Trademark (%) test 100 Polyalminum-Paho#2S 0.025 ◯ hydroxide

[0382] As seen from the above examples, any of the carboxylated latexfilms according to the present invention was non-adhesive.

[0383] Industrial Applicability

[0384] The present invention provides a powder-free and non-adhesivelatex product by adding a carboxyl-group blocking agent into acarboxylated latex, or alternatively by providing a layer treated withthe carboxyl-group blocking agent to one or both surfaces of thecarboxylated latex product. The present invention also enables tomanufacture a non-adhesive latex product having excellent durability ifthe carboxylated latex contains an internally added aluminum typeinorganic crosslinking agent, such as aluminate or aluminum hydroxidegel. In case of a fingerstall, a non-powdered machine-wound product canbe prepared on-machine utilizing non-adhesion of the product.

1. A non-adhesive carboxylated latex product incorporated with acarboxyl-group blocking agent.
 2. A non-adhesive carboxylated latexproduct having a layer treated with a carboxyl-group blocking agent onone or both surfaces of a carboxylated latex product or a carboxylatedlatex product incorporated with a carboxyl group blocking agent.
 3. Anon-adhesive carboxylated latex product having a layer treated with acarboxyl group blocking agent on the inside surface of a carboxylatedlatex product or a carboxylated latex product incorporated with acarboxyl group blocking agent and having a chlorination treatment on theoutside surface.
 4. A non-adhesive carboxylated latex product accordingto claim 1 to claim 3, wherein the carboxylated latex is NBR, SBR, CR orMBR.
 5. A durable, non-adhesive carboxylated latex product according toany one of claims 1 to 4, wherein the carboxylated latex is added withan internally added aluminum type inorganic crosslinking agent and iscrosslinked therewith.
 6. A non-adhesive carboxylated latex productaccording to any one of claims 1 to 5, wherein the latex product is adip product.
 7. A non-adhesive carboxylated latex product according toclaim 6, wherein the dip product is a fingerstall, gloves, balloon orcondom.
 8. A non-adhesive carboxylated latex product according to anyone of claims 1 to 7, wherein the carboxyl-group blocking agent is ametal element crosslinking agent having three or more valences.
 9. Anon-adhesive carboxylated latex product according to claim 8, whereinthe metal element crosslinking agent having three or more valencesincludes at least one selected from aluminum, titanium or zirconiumcompounds.
 10. A non-adhesive carboxylated latex product according toany one of claims 1 to 7, wherein the carboxyl-group blocking agent isan organic crosslinking agent for the carboxyl group of the carboxylatedlatex.
 11. A non-adhesive carboxylated latex product according to claim10, wherein the organic crosslinking agent for the carboxyl groupincludes at least one selected from aziridine compounds, epoxy componds,blocked isocyanates, oxazoline compounds, carbodiimido compounds,melamineformaldehyde resins, ureaformaldehyde resins, isocyanates,phenolformaldehyde resins, glycols, polyols, diamines, polyamines,hexamethoxymethylmelamines and methylolacrylamides.
 12. A non-adhesivecarboxylated latex product according to any one of claims 1 to 7,wherein the carboxyl-group blocking agent includes at least one selectedfrom glyoxals, polyamide compounds, polyamide polyurea compounds,polyamine polyurea compounds, polyamideamine polyurea compounds,polyamide polyurea glyoxal condensation reaction products,polyamideamine compounds, polyamideamine epihalohydrine condensationreaction products, polyamideamine formaldehyde condensation reactionproducts, polyamine epihalohydrine condensation reaction products,polyamine formaldehyde condensation reaction products, polyamidepolyurea epihalohydrine condensation reaction products, polyamidepolyurea formaldehyde condensation reaction products, polyamine polyureaepihalohydrine condensation reaction products, polyamine polyureaformaldehyde condensation reaction products, polyamideamine polyureaepihalohydrine condensation reaction products, and polyamideaminepolyurea formaldehyde condensation reaction products.
 13. A non-adhesivecarboxylated latex product according to any one of claims 1 to 7,wherein the carboxyl-group blocking agent includes at least one selectedfrom monofunctional amines, monofunctional epoxy compounds,monofunctional isocyanates and monofunctional blocked isocyanates.
 14. Anon-adhesive carboxylated latex product according to any one of claims 1to 7, wherein the carboxyl-group blocking agent is a sizing agent.
 15. Anon-adhesive carboxylated latex product according to any one of claims 1to 7, wherein the carboxyl-group blocking agent is a non-adhesivesurfactant.
 16. A method for producing a non-adhesive carboxylated latexproduct according to any one of claims 1 to 15, characterized in thatone or both surfaces of the latex product are brought into contact withone or more of the carboxyl-group blocking agent solutions defined inany of claims 8 to 15 to attach the carboxyl-group blocking agent to thelatex surface.
 17. A method for producing a non-adhesive carboxylatedlatex dip product, characterized in that there is used a solution of amono- or bi-valent external coagulant for carboxylated latex which ismixed with or dissolved in one or more of the carboxyl group blockingagents defined in any of claims 8 to
 15. 18. A method for producing anon-adhesive carboxylated latex dip product, characterized in that adipping former is dipped and deposited with one or more of thecarboxyl-group blocking agents defined in claims 8 to 15, dipped anddeposited with a mono- or bi-valent external coagulant, and then dippedin a latex.
 19. A method for producing a non-adhesive carboxylated latexdip product, characterized in that a dipping former is dipped anddeposited with one or more of the carboxyl-group blocking agents definedin any of claims 8 to 15, then dipped in a latex liquid to form a latexfilm, further dipped in a mono- or bi-valent external coagulantsolution, and subsequently dipped in the carboxylated latex again.
 20. Amethod for producing a non-adhesive carboxylated latex dip product,characterize in that a dipping former is dipped in a mixture of one ormore of the carboxyl-group blocking agents defined in any of claims 8 to15 and a carboxylated latex stable to the blocking agent to form a latexfilm, further dipped in a mono- or bi-valent external coagulantsolution, and thereafter dipped in the carboxylated latex liquid again.21. A method for producing a non-adhesive carboxylated latex dipproduct, characterized in that a dipping former is dipped in a mono- orbi-valent coagulant suspension for carboxylated latex which contains, asthe carrier, fine powder of one or more of the carboxyl-group blockingagents defined in any of claims 8 to 15 that is hardly soluble orinsoluble in water or alcohol, and subsequently dipped in thecarboxylated latex liquid.
 22. A non-adhesive fingerstall, wherein thefingerstall defined in claim 7 has a shape mechanically wound from themouth before removed from the dipping former.
 23. A non-adhesivefingerstall according to claim 7 or claim 22 which has a wound mouth.24. A method for producing a non-adhesive fingerstall with wound mouthaccording to claim 23, characterized in that an adhesive portion isprovided on the upper part at the time of dipping and then winding isconducted.
 25. A method for producing a non-adhesive fingerstallaccording to claim 7 or claim 22, characterized in that the outsidesurface is treated with a carboxyl group blocking agent after a woundmouth is provided.